Polyethylene composition and film

ABSTRACT

In some embodiments disclosed herein are polyethylene composition including a first polyethylene which is an ethylene copolymer having a weight average molecular weight of from 70,000 to 250,000 and a molecular weight distribution Mw/Mn of &lt;2.3, a second polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of less than 75,000 and a molecular weight distribution Mw/Mn of &lt;2.3, a third polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of less than 75,000 and a molecular weight distribution Mw/Mn of &lt;2.3, and a fourth polyethylene which is an ethylene copolymer or homopolymer having a weight average molecular weight of from 100,000 to 250,000 and a molecular weight distribution Mw/Mn of &gt;2.3, where the first polyethylene has more short chain branching than the second polyethylene or the third polyethylene. The polyethylene composition may have a soluble fraction in a CEF analysis of at least 7.5 weight percent. Film made from the polyethylene composition may have a machine direction 1% secant modulus of ≥200 MPa (at a film thickness of about 1 mil) and an oxygen transmission rate (OTR) of ≥550 cm3 per 100 inch2 (at a film thickness of about 1 mil). Film made from the polyethylene composition retains much of its dart impact performance on downgauging from a thickness of 1 mil to a thickness of 0.75 mil.

This application claims the benefit of the earlier filing date ofCanadian Application Serial Number 3011041 filed on Jul. 11, 2018, whichapplication is incorporated herein by reference in its entirety.

The present disclosure provides polyethylene compositions which whenblown into film have good stiffness, good oxygen permeability and havean ability to retain dart impact performance when downgauging. Thepolyethylene compositions include three polyethylene components whichare made with a single site polymerization catalyst and one polyethylenecomponent which is made with multi-site polymerization catalysts.

Multicomponent polyethylene compositions are well known in the art. Onemethod to access multicomponent polyethylene compositions is to use twoor more distinct polymerization catalysts in one or more polymerizationreactors. For example, the use of single site and Ziegler-Natta typepolymerization catalysts in at least two distinct solutionpolymerization reactors is known. Such reactors may be configured inseries or in parallel.

Solution polymerization processes are generally carried out attemperatures above the melting point of the ethylene homopolymer orcopolymer product being made. In a typical solution polymerizationprocess, catalyst components, solvent, monomers and hydrogen are fedunder pressure to one or more reactors.

For solution phase ethylene polymerization, or ethylenecopolymerization, reactor temperatures can range from about 80° C. toabout 300° C. while pressures generally range from about 3 MPag to about45 MPag. The ethylene homopolymer or copolymer produced remainsdissolved in the solvent under reactor conditions. The residence time ofthe solvent in the reactor is relatively short, for example, from about1 second to about 20 minutes. The solution process can be operated undera wide range of process conditions that allow the production of a widevariety of ethylene polymers. Post reactor, the polymerization reactionis quenched to prevent further polymerization, by adding a catalystdeactivator, and optionally passivated, by adding an acid scavenger.Once deactivated (and optionally passivated), the polymer solution ispassed to a polymer recovery operation (a devolatilization system) wherethe ethylene homopolymer or copolymer is separated from process solvent,unreacted residual ethylene and unreacted optional α-olefin(s).

Regardless of the manner of production, there remains a need to improvethe performance of multicomponent polyethylene compositions in filmapplications.

The present disclosure provides polyethylene compositions which whenmade into film have a good balance of stiffness and oxygen transmissionrates, as well as downgauging properties.

An embodiment of the disclosure is a polyethylene composition including:

from 15 to 75 wt. % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight Mw of from 70,000 to 250,000, a molecular weight distributionM_(w)/M_(n) of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt. % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight Mw of less than 75,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; and

from 5 to 50 wt. % of a third polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight Mw of less than 75,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; and

from 5 to 60 wt. % of a fourth polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the fourth polyethylene having aweight average molecular weight Mw of from 100,000 to 250,000, amolecular weight distribution M_(w)/M_(n) of >2.3 and from 0 to 75 shortchain branches per thousand carbon atoms; wherein

the number of short chain branches per thousand carbon atoms in thefirst polyethylene (SCB_(PE-1)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)), the third polyethylene (SCB_(PE-3)) and the fourthpolyethylene (SCB_(PE-4));

the number of short chain branches per thousand carbon atoms in thefourth polyethylene (SCB_(PE-4)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3));

the weight average molecular weight of the second polyethylene and thethird polyethylene are less than the weight average molecular weight ofthe first polyethylene and the fourth polyethylene; and

the weight average molecular weight of the second polyethylene and thethird polyethylene are within 20,000 units of each other; wherein, thepolyethylene composition has a density of ≤0.939 g/cm³, and a melt indexI₂ of from 0.1 to 10 dg/min.

In an embodiment of the disclosure a polyethylene composition has asoluble fraction in a crystallization elution fractionation (CEF)analysis of at least 7.5 weight percent.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, including a polyethylene composition including:

from 15 to 75 wt. % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight Mw of from 70,000 to 250,000, a molecular weight distributionM_(w)/M_(n) of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt. % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight Mw of less than 75,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; and

from 5 to 50 wt. % of a third polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight Mw of less than 75,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; and

from 5 to 60 wt. % of a fourth polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the fourth polyethylene having aweight average molecular weight Mw of from 100,000 to 250,000, amolecular weight distribution M_(w)/M_(n) of >2.3 and from 0 to 75 shortchain branches per thousand carbon atoms; wherein

the number of short chain branches per thousand carbon atoms in thefirst polyethylene (SCB_(PE-1)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)), the third polyethylene (SCB_(PE-3)) and the fourthpolyethylene (SCB_(PE-4));

the number of short chain branches per thousand carbon atoms in thefourth polyethylene (SCB_(PE-4)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3));

the weight average molecular weight of the second polyethylene and thethird polyethylene are less than the weight average molecular weight ofthe first polyethylene and the fourth polyethylene; and

the weight average molecular weight of the second polyethylene and thethird polyethylene are within 20,000 units of each other; wherein,

the polyethylene composition has a density of ≤0.939 g/cm³, and a meltindex I₂ of from 0.1 to 10 dg/min.

In an embodiment, a film layer has a first dart impact value whenmeasured at a film thickness of about 1 mil, and a second dart impactvalue when measured at a film thickness of about 0.75 mil, wherein thesecond dart impact value is within 20 percent of the first dart impactvalue.

In an embodiment, a film layer has a machine direction (MD) 1% secantmodulus of ≥200 MPa when measured at a film thickness of about 1 mil.

In an embodiment, a film layer has an oxygen transmission rate (OTR) of≥550 cm³ per 100 inch² when measured at a film thickness of about 1 mil.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, wherein the film layer has a has a machine direction(MD) 1% secant modulus of ≥200 MPa when measured at a film thickness ofabout 1 mil, and an oxygen transmission rate (OTR) of ≥550 cm³ per 100inch² when measured at a film thickness of about 1 mil.

An embodiment of the disclosure is a film layer having a thickness offrom 0.5 to 10 mil, wherein the film layer satisfies the followingrelationship:

oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 shows the gel permeation chromatographs (GPC) with refractiveindex detection of polyethylene compositions made according to thepresent disclosure as well as for some comparative polyethylenes.

FIG. 2 shows the gel permeation chromatographs with Fourier transforminfra-red (GPC-FTIR) detection obtained for polyethylene compositionsmade according to the present disclosure as well as for some comparativepolyethylenes. The comonomer content, shown as the number of short chainbranches per 1000 carbons (y-axis), is given relative to the copolymermolecular weight (x-axis). The upwardly sloping line (from left toright) is the short chain branching (in short chain branches per 1000carbons atoms) determined by FTIR. As can be seen in the Figure, forInventive Examples 1, 2 and 3 the number of short chain branchesinitially increases at higher molecular weights and then decreases againat still higher molecular weights, and hence the comonomer incorporationis said to be “partially reversed” with a peak or maximum present.

FIG. 3 shows the differential scanning calorimetry analysis (DSC) andprofile of polyethylene compositions made according to the presentdisclosure as well as for some comparative polyethylenes.

FIG. 4 shows a plot of the equation: OTR=−5.4297 (machine direction (MD)1% secant modulus)+1767.8. The values for the OTR (the y-axis) areplotted against the corresponding machine direction (MD) 1% secantmodulus values (the x-axis) for films made from the polyethylenecompositions of the present disclosure as well as those for films madefrom several comparative polyethylenes. “1/2.5 film” means that the filmwas made at 1 mil of thickness with a blow up ratio (BUR) of 2.5.

FIG. 5 shows a plot of the dart impact strength (y-axis) against thecorresponding machine direction (MD) 1% secant modulus values (thex-axis) for films made from the polyethylene compositions of the presentdisclosure as well as those for films made from several comparativepolyethylenes at two different film thicknesses: a film gauge of 1 mil,and a film gauge of 0.75 mil.

DEFINITION OF TERMS

Other than in the examples or where otherwise indicated, all numbers orexpressions referring to quantities of ingredients, extrusionconditions, etc., used in the specification and claims are to beunderstood as modified in all instances by the term “about”.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the desired properties thatthe various embodiments desire to obtain. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. The numerical values set forth inthe specific examples are reported as precisely as possible. Anynumerical values, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

It should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

In order to form a more complete understanding of this disclosure thefollowing terms are defined and should be used with the accompanyingfigures and the description of the various embodiments throughout.

As used herein, the term “monomer” refers to a small molecule that maychemically react and become chemically bonded with itself or othermonomers to form a polymer.

As used herein, the term “α-olefin” or “alpha-olefin” is used todescribe a monomer having a linear hydrocarbon chain containing from 3to 20 carbon atoms having a double bond at one end of the chain; anequivalent term is “linear α-olefin”.

As used herein, the term “polyethylene” or “ethylene polymer”, refers tomacromolecules produced from ethylene monomers and optionally one ormore additional monomers; regardless of the specific catalyst orspecific process used to make the ethylene polymer. In the polyethyleneart, the one or more additional monomers are called “comonomer(s)” andoften include α-olefins. The term “homopolymer” refers to a polymer thatcontains only one type of monomer. An “ethylene homopolymer” is madeusing only ethylene as a polymerizable monomer. The term “copolymer”refers to a polymer that contains two or more types of monomer. An“ethylene copolymer” is made using ethylene and one or more other typesof polymerizable monomer. Common polyethylenes include high densitypolyethylene (HDPE), medium density polyethylene (MDPE), linear lowdensity polyethylene (LLDPE), very low density polyethylene (VLDPE),ultralow density polyethylene (ULDPE), plastomer and elastomers. Theterm polyethylene also includes polyethylene terpolymers which mayinclude two or more comonomers in addition to ethylene. The termpolyethylene also includes combinations of, or blends of, thepolyethylenes described above.

The term “heterogeneously branched polyethylene” refers to a subset ofpolymers in the ethylene polymer group that are produced using aheterogeneous catalyst system; non-limiting examples of which includeZiegler-Natta or chromium catalysts, both of which are well known in theart.

The term “homogeneously branched polyethylene” refers to a subset ofpolymers in the ethylene polymer group that are produced usingsingle-site catalysts; non-limiting examples of which includemetallocene catalysts, phosphinimine catalysts, and constrained geometrycatalysts all of which are well known in the art.

Typically, homogeneously branched polyethylene has narrow molecularweight distributions, for example gel permeation chromatography (GPC)M_(w)/M_(n) values of less than 2.8, or, for example, less than about2.3, although exceptions may arise; M_(w) and M_(n) refer to weight andnumber average molecular weights, respectively. In contrast, theM_(w)/M_(n) of heterogeneously branched ethylene polymers are typicallygreater than the M_(w)/M_(n) of homogeneous polyethylene. In general,homogeneously branched ethylene polymers also have a narrow comonomerdistribution, i.e., each macromolecule within the molecular weightdistribution has a similar comonomer content. Frequently, thecomposition distribution breadth index “CDBI” is used to quantify howthe comonomer is distributed within an ethylene polymer, as well as todifferentiate ethylene polymers produced with different catalysts orprocesses. The “CDBI₅₀” is defined as the percent of ethylene polymerwhose composition is within 50 weight percent (wt. %) of the mediancomonomer composition; this definition is consistent with that describedin WO 93/03093 assigned to Exxon Chemical Patents Inc. The CDBI₅₀ of anethylene interpolymer can be calculated from TREF curves (TemperatureRising Elution Fractionation); the TREF method is described in Wild, etal., J. Polym. Sci., Part B, Polym. Phys., Vol. 20 (3), pages 441-455.Typically, the CDBI₅₀ of homogeneously branched ethylene polymers aregreater than about 70% or greater than about 75%. In contrast, theCDBI₅₀ of α-olefin containing heterogeneously branched ethylene polymersare generally lower than the CDBI₅₀ of homogeneous ethylene polymers.For example, the CDBI₅₀ of a heterogeneously branched ethylene polymermay be less than about 75%, or less than about 70%.

It is well known to those skilled in the art, that homogeneouslybranched ethylene polymers are frequently further subdivided into“linear homogeneous ethylene polymers” and “substantially linearhomogeneous ethylene polymers”. These two subgroups differ in the amountof long chain branching: for example, linear homogeneous ethylenepolymers have less than about 0.01 long chain branches per 1000 carbonatoms; while substantially linear ethylene polymers have greater thanabout 0.01 to about 3.0 long chain branches per 1000 carbon atoms. Along chain branch is macromolecular in nature, i.e. similar in length tothe macromolecule that the long chain branch is attached to. Hereafter,in this disclosure, the term “homogeneously branched polyethylene” or“homogeneously branched ethylene polymer” refers to both linearhomogeneous ethylene polymers and substantially linear homogeneousethylene polymers.

The term “thermoplastic” refers to a polymer that becomes liquid whenheated, will flow under pressure and solidify when cooled. Thermoplasticpolymers include ethylene polymers as well as other polymers used in theplastic industry; non-limiting examples of other polymers commonly usedin film applications include barrier resins (EVOH), tie resins,polyethylene terephthalate (PET), polyamides and the like.

As used herein the term “monolayer film” refers to a film containing asingle layer of one or more thermoplastics.

As used herein, the terms “hydrocarbyl”, “hydrocarbyl radical” or“hydrocarbyl group” refers to linear or cyclic, aliphatic, olefinic,acetylenic and aryl (aromatic) radicals including hydrogen and carbonthat are deficient by one hydrogen.

As used herein, an “alkyl radical” includes linear, branched and cyclicparaffin radicals that are deficient by one hydrogen radical;non-limiting examples include methyl (—CH₃) and ethyl (—CH₂CH₃)radicals. The term “alkenyl radical” refers to linear, branched andcyclic hydrocarbons containing at least one carbon-carbon double bondthat is deficient by one hydrogen radical.

As used herein, the term “aryl” group includes phenyl, naphthyl, pyridyland other radicals whose molecules have an aromatic ring structure;non-limiting examples include naphthylene, phenanthrene and anthracene.An “arylalkyl” group is an alkyl group having an aryl group pendantthere from; non-limiting examples include benzyl, phenethyl andtolylmethyl; an “alkylaryl” is an aryl group having one or more alkylgroups pendant there from; non-limiting examples include tolyl, xylyl,mesityl and cumyl.

As used herein, the phrase “heteroatom” includes any atom other thancarbon and hydrogen that can be bound to carbon. A“heteroatom-containing group” is a hydrocarbon radical that contains aheteroatom and may contain one or more of the same or differentheteroatoms. In one embodiment, a heteroatom-containing group is ahydrocarbyl group containing from 1 to 3 atoms chosen from boron,aluminum, silicon, germanium, nitrogen, phosphorous, oxygen and sulfur.Non-limiting examples of heteroatom-containing groups include radicalsof imines, amines, oxides, phosphines, ethers, ketones, oxoazolinesheterocyclics, oxazolines, thioethers, and the like. The term“heterocyclic” refers to ring systems having a carbon backbone thatinclude from 1 to 3 atoms chosen from boron, aluminum, silicon,germanium, nitrogen, phosphorous, oxygen and sulfur.

As used herein the term “unsubstituted” means that hydrogen radicals arebounded to the molecular group that follows the term unsubstituted. Theterm “substituted” means that the group following this term possessesone or more moieties that have replaced one or more hydrogen radicals inany position within the group; non-limiting examples of moieties includehalogen radicals (F, Cl, Br), hydroxyl groups, carbonyl groups, carboxylgroups, amine groups, phosphine groups, alkoxy groups, phenyl groups,naphthyl groups, C₁ to C₃₀ alkyl groups, C₂ to C₃₀ alkenyl groups, andcombinations thereof. Non-limiting examples of substituted alkyls andaryls include: acyl radicals, alkylamino radicals, alkoxy radicals,aryloxy radicals, alkylthio radicals, dialkylamino radicals,alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbornoyl radicals,alkyl- and dialkyl-carbamoyl radicals, acyloxy radicals, acylaminoradicals, arylamino radicals and combinations thereof.

In the present disclosure, the polyethylene compositions include atleast the following types of polymers: a first polyethylene which is anethylene copolymer and which has a Mw/Mn of less than about 2.3; asecond polyethylene which is an ethylene copolymer or an ethylenehomopolymer which is different from the first polyethylene and which hasa Mw/Mn of less than about 2.3; a third polyethylene which is anethylene copolymer or an ethylene homopolymer which is different fromthe first polyethylene and which has a Mw/Mn of less than about 2.3, anda fourth polyethylene which is an ethylene copolymer or an ethylenehomopolymer which has a Mw/Mn of greater than about 2.3. Each of thesepolyethylene components, and the polyethylene composition of which theyare each a part are further described below.

The First Polyethylene

In an embodiment of the disclosure, the first polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the first polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the first polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the first polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the first polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by formula:

(L^(A))_(a)M(PI)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from Ti, Zr, and Hf; PI represents a phosphinimineligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2;(a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of themetal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, PI, is defined by formula:

(R^(p))₃P═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the first polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the first polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the first polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable”, means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure the single site catalyst used to makethe first polyethylene has isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are included of a cation and a bulky anion;wherein the latter is substantially non-coordinating. Non-limitingexamples of ionic activators are boron ionic activators that are fourcoordinate with four ligands bonded to the boron atom. Non-limitingexamples of boron ionic activators include the following formulas shownbelow;

[R⁵]⁺[B(R⁷)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[(R₈)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting examples of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene produces no long chain branches, and thefirst polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the first polyethylene produces long chain branches, and the firstpolyethylene will contain long chain branches, hereinafter “LCB”. LCB isa well-known structural phenomenon in polyethylenes and well known tothose of ordinary skill in the art. Traditionally, there are threemethods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the first polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the first polyethylene may be about 1.4, orabout 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the first polyethylene has a molecularweight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 or about 2.0.In embodiments of the disclosure, the first polyethylene has a molecularweight distribution, M_(w)/M_(n) of from about 1.7 to about 2.2.

In an embodiment of the disclosure, the first polyethylene has from 1 to200 short chain branches per thousand carbon atoms (SCB_(PE-1)). Infurther embodiments, the first polyethylene has from 3 to 150 shortchain branches per thousand carbon atoms (SCB_(PE-1)), or from 5 to 100short chain branches per thousand carbon atoms (SCB_(PE-1)), or from 10to 100 short chain branches per thousand carbon atoms (SCB_(PE-1)), orfrom 5 to 75 short chain branches per thousand carbon atoms(SCB_(PE-1)), or from 10 to 75 short chain branches per thousand carbonatoms (SCB_(PE-1)), or from 15 to 75 short chain branches per thousandcarbon atoms (SCB_(PE-1)), or from 20 to 75 short chain branches perthousand carbon atoms (SCB_(PE-1)). In still further embodiments, thefirst polyethylene has from 20 to 100 short chain branches per thousandcarbon atoms (SCB_(PE-1)), or from 25 to 100 short chain branches perthousand carbon atoms (SCB_(PE-1)), or from 25 to 80 short chainbranches per thousand carbon atoms (SCB_(PE-1)), or from 30 to 100 shortchain branches per thousand carbon atoms (SCB_(PE-1)), or from 30 to 75short chain branches per thousand carbon atoms (SCB_(PE-1)), or from 25to 75 short chain branches per thousand carbon atoms (SCB_(PE-1)), orfrom 25 to 60 short chain branches per thousand carbon atoms(SCB_(PE-1)), or from 25 to 50 short chain branches per thousand carbonatoms (SCB_(PE-1)), or from 30 to 60 short chain branches per thousandcarbon atoms (SCB_(PE-1)), or from 25 to 55 short chain branches perthousand carbon atoms (SCB_(PE-1)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-1)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in the second polyethylene (SCB_(PE-2)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in the third polyethylene (SCB_(PE-3)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in the fourth polyethylene (SCB_(PE-4)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in each of the second polyethylene (SCB_(PE-2)), and the thirdpolyethylene (SCB_(PE-3)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the first polyethylene (SCB_(PE-1)), isgreater than the number of short chain branches per thousand carbonatoms in each of the second polyethylene (SCB_(PE-2)), the thirdpolyethylene (SCB_(PE-3)) and the fourth polyethylene (SCB_(PE-4)).

In embodiments of the disclosure, the upper limit on the density, d1 ofthe first polyethylene may be about 0.975 g/cm³; in some cases about0.965 g/cm³ and; in other cases about 0.955 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d1 of the first polyethylenemay be about 0.855 g/cm³, in some cases about 0.865 g/cm³, and; in othercases about 0.875 g/cm³.

In embodiments of the disclosure the density, d1 of the firstpolyethylene may be from about 0.855 to about 0.965 g/cm³, or from about0.865 g/cm³ to about 0.965 g/cm³, or from about 0.870 g/cm³ to about0.960 g/cm³, or from about 0.865 g/cm³ to about 0.950 g/cm³, or fromabout 0.865 g/cm³ to about 0.940 g/cm³, or from about 0.865 g/cm³ toabout 0.936 g/cm³, or from about 0.860 g/cm³ to about 0.932 g/cm³, orfrom about 0.865 g/cm³ to about 0.926 g/cm³, or from about 0.865 g/cm³to about 0.921 g/cm³, or from about 0.865 g/cm³ to about 0.918 g/cm³, orfrom about 0.865 g/cm³ to about 0.916 g/cm³, or from about 0.870 g/cm³to about 0.916 g/cm³, or from about 0.865 g/cm³ to about 0.912 g/cm³, orfrom about 0.865 g/cm³ to about 0.910 g/cm³, or from about 0.865 g/cm³to about 0.905 g/cm³, or from about 0.865 g/cm³ to about 0.900 g/cm³, orfrom about 0.855 g/cm³ to about 0.900 g/cm³, or from about 0.855 g/cm³to about 0.905 g/cm³, or from about 0.855 g/cm³ to about 0.910 g/cm³, orfrom about 0.855 g/cm³ to about 0.916 g/cm³.

In embodiments of the disclosure, the upper limit on the CDBI₅₀ of thefirst polyethylene may be about 98 weight %, in other cases about 95 wt% and in still other cases about 90 wt. %. In embodiments of thedisclosure, the lower limit on the CDBI₅₀ of the first polyethylene maybe about 70 weight %, in other cases about 75 wt % and in still othercases about 80 wt. %.

In embodiments of the disclosure, the melt index of the firstpolyethylene I₂ ¹ may be from about 0.01 dg/min to about 1000 dg/min, orfrom about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or less than about 5 dg/min, or less than about 3 dg/min, orless than about 1.0 dg/min, or less than about 0.75 dg/min.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) of from about 50,000 to about 300,000,or from about 50,000 to about 250,000, or from about 60,000 to about250,000, or from about 70,000 to about 250,000 or from about 60,000 toabout 220,000, or from about 70,000 to about 200,000, or from about75,000 to about 200,000, or from about 75,000 to about 195,000, or fromabout 75,000 to about 190,000, or from about 75,000 to about 175,000; orfrom about 70,000 to about 175,000, or from about 70,000 to about150,000.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the second polyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the third polyethylene.

In an embodiment of the disclosure, the first polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of both the second polyethylene and the thirdpolyethylene.

In embodiments of the disclosure, the upper limit on the weight percent(wt %) of the first polyethylene in the polyethylene composition (i.e.the weight percent of the first polyethylene based on the total weightof the first, the second, the third and the fourth polyethylene) may beabout 80 wt. %, or about 75 wt. %, or about 70 wt. %, or about 65 wt. %,or about 60 wt. %, or about 55 wt. % or about 50 wt. %, or about 45 wt.%, or about 40 wt. %, or about 35%. In embodiments of the disclosure,the lower limit on the wt. % of the first polyethylene in thepolyethylene composition may be about 1 wt. %, or about 5 wt. %, orabout 10 wt. %, or about 15 wt. %, or about 20 wt. %, or about 25 wt. %or in other cases about 30 wt. %.

The Second Polyethylene

In an embodiment of the disclosure, the second polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the second polyethylene is anethylene homopolymer.

In an embodiment of the disclosure, the second polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the second polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the second polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the second polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by formula:

(L^(A))_(a)M(PI)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from Ti, Zr, and Hf; PI represents a phosphinimineligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2;(a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of themetal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, PI, is defined by formula:

(R^(p))₃P═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the second polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the second polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the second polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable”, means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure the single site catalyst used to makethe second polyethylene has isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are included of a cation and a bulky anion;wherein the latter is substantially non-coordinating. Non-limitingexamples of ionic activators are boron ionic activators that are fourcoordinate with four ligands bonded to the boron atom. Non-limitingexamples of boron ionic activators include the following formulas shownbelow;

[R⁵]⁺[B(R⁷)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron,N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron,di-(isopropyl)ammonium tetra(pentafluorophenyl)boron,dicyclohexylammonium tetra(phenyl)boron, triphenylphosphoniumtetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron,tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropilliumtetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting example of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene produces no long chain branches, and thesecond polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the second polyethylene produces long chain branches, and thesecond polyethylene will contain long chain branches, hereinafter “LCB”.LCB is a well-known structural phenomenon in polyethylenes and wellknown to those of ordinary skill in the art. Traditionally, there arethree methods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the second polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the second polyethylene may be about 1.4,or about 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the second polyethylene has amolecular weight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 orabout 2.0. In embodiments of the disclosure, the second polyethylene hasa molecular weight distribution, M_(w)/M_(n) of from about 1.7 to about2.2.

In an embodiment of the disclosure, the second polyethylene has from 0to 100 short chain branches per thousand carbon atoms (SCB_(PE-2)). Infurther embodiments, the second polyethylene has from 0 to 30 shortchain branches per thousand carbon atoms (SCB_(PE-2)), or from 0 to 20short chain branches per thousand carbon atoms (SCB_(PE-2)), or from 0to 15 short chain branches per thousand carbon atoms (SCB_(PE-2)), orfrom 0 to 10 short chain branches per thousand carbon atoms(SCB_(PE-2)), or from 0 to 5 short chain branches per thousand carbonatoms (SCB_(PE-2)), or fewer than 5 short chain branches per thousandcarbon atoms (SCB_(PE-2)), or fewer than 3 short chain branches perthousand carbon atoms (SCB_(PE-2)), or fewer than 1 short chain branchesper thousand carbon atoms (SCB_(PE-2)), or about zero short chainbranches per thousand carbon atoms (SCB_(PE-2)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-2)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In embodiments of the disclosure, the upper limit on the density, d2 ofthe second polyethylene may be about 0.985 g/cm³; in some cases about0.975 g/cm³ and; in other cases about 0.965 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d2 of the secondpolyethylene may be about 0.921 g/cm³, in some cases about 0.932 g/cm³,and; in other cases about 0.949 g/cm³.

In embodiments of the disclosure the density, d2 of the secondpolyethylene may be from about 0.921 g/cm³ to about 0.980 g/cm³, or fromabout 0.921 g/cm³ to about 0.975 g/cm³, or from about 0.926 g/cm³ toabout 0.975 g/cm³, or from about 0.930 g/cm³ to about 0.975 g/cm³, orfrom about 0.936 g/cm³ to about 0.975 g/cm³, or from about 0.940 g/cm³to about 0.975 g/cm³, or from about 0.940 g/cm³ to about 0.980 g/cm³, orfrom about 0.945 g/cm³ to about 0.975 g/cm³, or from about 0.950 g/cm³to about 0.975 g/cm³, or from about 0.951 g/cm³ to about 0.975 g/cm³, orfrom about 0.953 g/cm³ to about 0.975 g/cm³, or from about 0.953 g/cm³to about 0.985 g/cm³.

In embodiments of the disclosure the melt index of the secondpolyethylene I₂ ² may be from about 0.1 dg/min to about 10000 dg/min, orfrom about 0.1 dg/min to about 5000 dg/min, or from about 1 dg/min toabout 10000 dg/min, or from about 1 dg/min to about 5000 dg/min, or fromabout 1 dg/min to about 2500 dg/min, or from about 1 dg/min to about2000 dg/min, or from about 10 dg/min to about 10000 dg/min, or fromabout 10 dg/min to about 5000 dg/min, or from about 10 dg/min to about2500 dg/min, or from about 25 dg/min to about 10000 dg/min, or fromabout 25 dg/min to about 5000 dg/min, or from about 25 dg/min to about2500 dg/min.

In an embodiment of the disclosure, the second polyethylene has a weightaverage molecular weight, M_(w) of from about 10,000 to about 150,000,or from about 10,000 to about 125,000, or from about 15,000 to about100,000, or from about 15,000 to about 90,000, or from about 15,000 toabout 80,000 or from about 20,000 to about 75,000, or from about 20,000to about 90,000, or from about 20,000 to about 80,000, or from about15,000 to about 75,000, or from about 10,000 to about 50,000, or fromabout 15,000 to about 40,000, or from about 12,000 to about 45,000, orfrom about 12,000 to about 40,000, or less than about 100,000 or lessthan about 75,000, or less than about 50,000, or less than about 45,000or less than about 40,000, or less than about 35,000, or less than about30,000.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the first polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the fourth polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene is less than the weight average molecularweight of the first polyethylene and the fourth polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 25,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 20,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 15,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 10,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 7,500units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 5,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the second polyethylene and the third polyethylene are within 2,500units (in g/mol) of each other.

In embodiments of the disclosure, the upper limit on the weight percent(wt. %) of the second polyethylene in the polyethylene composition (i.e.the weight percent of the second polyethylene based on the total weightof the first, the second, the third and the fourth polyethylene) may beabout 75 wt. %, or about 70 wt. %, or about 65 wt. %, or about 60 wt. %,or about 55 wt. %, or about 50 wt. %, or about 45 wt. %, or about 40 wt.% or about 35 wt. %. In embodiments of the disclosure, the lower limiton the wt. % of the second polyethylene in the polyethylene compositionmay be about 1 wt. %, or 5 wt. %, or about 10 wt. %, or about 15 wt. %,or about 20 wt. %.

The Third Polyethylene

In an embodiment of the disclosure, the third polyethylene is made witha single site catalyst, non-limiting examples of which includephosphinimine catalysts, metallocene catalysts, and constrained geometrycatalysts, all of which are well known in the art.

In an embodiment of the disclosure, the third polyethylene is anethylene homopolymer.

In an embodiment of the disclosure, the third polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to make an ethylene copolymer include 1-propene, 1-butene,1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the third polyethylene is ahomogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the third polyethylene is anethylene/1-octene copolymer.

In an embodiment of the disclosure, the third polyethylene is made witha phosphinimine catalyst.

In an embodiment of the disclosure, a phosphinimine catalyst isrepresented by formula:

(L^(A))_(a)M(PI)_(b)(Q)_(n)

wherein (L^(A)) represents is cyclopentadienyl-type ligand; M representsa metal atom chosen from Ti, Zr, and Hf; PI represents a phosphinimineligand; Q represents an activatable ligand; a is 0 or 1; b is 1 or 2;(a+b)=2; n is 1 or 2, and; the sum of (a+b+n) equals the valance of themetal M.

As used herein, the term “cyclopentadienyl-type” ligand is meant toinclude ligands which contain at least one five-carbon ring which isbonded to the metal via eta-5 (or in some cases eta-3) bonding. Thus,the term “cyclopentadienyl-type” includes, for example, unsubstitutedcyclopentadienyl, singly or multiply substituted cyclopentadienyl,unsubstituted indenyl, singly or multiply substituted indenyl,unsubstituted fluorenyl and singly or multiply substituted fluorenyl.Hydrogenated versions of indenyl and fluorenyl ligands are alsocontemplated for use in the current disclosure, so long as thefive-carbon ring which bonds to the metal via eta-5 (or in some caseseta-3) bonding remains intact. Substituents for a cyclopentadienylligand, an indenyl ligand (or hydrogenated version thereof) and afluorenyl ligand (or hydrogenated version thereof) may be chosen from aC₁₋₃₀ hydrocarbyl radical (which hydrocarbyl radical may beunsubstituted or further substituted by for example a halide and/or ahydrocarbyl group; for example a suitable substituted C₁₋₃₀ hydrocarbylradical is a pentafluorobenzyl group such as —CH₂C₆F₅); a halogen atom;a C₁₋₈ alkoxy radical; a C₆₋₁₀ aryl or aryloxy radical (each of whichmay be further substituted by for example a halide and/or a hydrocarbylgroup); an amido radical which is unsubstituted or substituted by up totwo C₁₋₈ alkyl radicals; a phosphido radical which is unsubstituted orsubstituted by up to two C₁₋₈ alkyl radicals; a silyl radical of theformula —Si(R′)₃ wherein each R′ is independently chosen from hydrogen,a C₁₋₈ alkyl or alkoxy radical, C₆₋₁₀ aryl or aryloxy radicals; and agermanyl radical of the formula —Ge(R′)₃ wherein R′ is as defineddirectly above.

The phosphinimine ligand, PI, is defined by formula:

(R^(p))₃P═N—

wherein the R^(p) groups are independently selected from: a hydrogenatom; a halogen atom; C₁₋₂₀ hydrocarbyl radicals which are unsubstitutedor substituted with one or more halogen atom(s); a C₁₋₈ alkoxy radical;a C₆₋₁₀ aryl radical; a C₆₋₁₀ aryloxy radical; an amido radical; a silylradical of formula —Si(R^(s))₃, wherein the R^(s) groups areindependently selected from, a hydrogen atom, a C₁₋₈ alkyl or alkoxyradical, a C₆₋₁₀ aryl radical, a C₆₋₁₀ aryloxy radical, or a germanylradical of formula —Ge(R^(G))₃, wherein the R^(G) groups are defined asR^(s) is defined in this paragraph.

In an embodiment of the disclosure, the metal, M in the phosphiniminecatalyst is titanium, Ti.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene is cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride, Cp((t-Bu)₃PN)TiCl₂.

In an embodiment of the disclosure, the third polyethylene is made witha metallocene catalyst.

In an embodiment of the disclosure, the third polyethylene is made witha bridged metallocene catalyst.

In an embodiment of the disclosure, the third polyethylene is made witha bridged metallocene catalyst having the formula I:

In Formula (I): M is a group 4 metal selected from titanium, zirconiumor hafnium; G is a group 14 element selected from carbon, silicon,germanium, tin or lead; R₁ is a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₂ and R₃are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; R₄ and R₅are independently selected from a hydrogen atom, a C₁₋₂₀ hydrocarbylradical, a C₁₋₂₀ alkoxy radical or a C₆₋₁₀ aryl oxide radical; and Q isindependently an activatable leaving group ligand.

In the current disclosure, the term “activatable”, means that the ligandQ may be cleaved from the metal center M via a protonolysis reaction orabstracted from the metal center M by suitable acidic or electrophiliccatalyst activator compounds (also known as “co-catalyst” compounds)respectively, examples of which are described below. The activatableligand Q may also be transformed into another ligand which is cleaved orabstracted from the metal center M (e.g. a halide may be converted to analkyl group). Without wishing to be bound by any single theory,protonolysis or abstraction reactions generate an active “cationic”metal center which can polymerize olefins.

In embodiments of the present disclosure, the activatable ligand, Q isindependently chosen from a hydrogen atom; a halogen atom; a C₁₋₂₀hydrocarbyl radical, a C₁₋₂₀ alkoxy radical, and a C₆₋₁₀ aryl or aryloxyradical, where each of the hydrocarbyl, alkoxy, aryl, or aryl oxideradicals may be un-substituted or further substituted by one or morehalogen or other group; a C₁₋₈ alkyl; a C₁₋₈ alkoxy; a C₆₋₁₀ aryl oraryloxy; an amido or a phosphido radical, but where Q is not acyclopentadienyl. Two Q ligands may also be joined to one another andform for example, a substituted or unsubstituted diene ligand (e.g.1,3-butadiene); or a delocalized heteroatom containing group such as anacetate or acetamidinate group. In a convenient embodiment of thedisclosure, each Q is independently chosen from a halide atom, a C₁₋₄alkyl radical and a benzyl radical. Particularly suitable activatableligands Q are monoanionic such as a halide (e.g. chloride) or ahydrocarbyl (e.g. methyl, benzyl).

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdichloride having the molecular formula: [(2,7-tBu₂Flu)Ph₂C(Cp)HfCl₂].

In an embodiment of the disclosure the single site catalyst used to makethe third polyethylene has isdiphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethyl having the molecular formula [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂].

In addition to the single site catalyst molecule per se, an activesingle site catalyst system may further include one or more of thefollowing: an alkylaluminoxane co-catalyst and an ionic activator. Thesingle site catalyst system may also optionally include a hinderedphenol.

Although the exact structure of alkylaluminoxane is uncertain, subjectmatter experts generally agree that it is an oligomeric species thatcontain repeating units of the general formula:

(R)₂AlO—(Al(R)—O)_(n)—Al(R)₂

where the R groups may be the same or different linear, branched orcyclic hydrocarbyl radicals containing 1 to 20 carbon atoms and n isfrom 0 to about 50. A non-limiting example of an alkylaluminoxane ismethylaluminoxane (or MAO) wherein each R group is a methyl radical.

In an embodiment of the disclosure, R of the alkylaluminoxane, is amethyl radical and m is from 10 to 40.

In an embodiment of the disclosure, the co-catalyst is modifiedmethylaluminoxane (MMAO).

It is well known in the art, that the alkylaluminoxane can serve dualroles as both an alkylator and an activator. Hence, an alkylaluminoxaneco-catalyst is often used in combination with activatable ligands suchas halogens.

In general, ionic activators are included of a cation and a bulky anion;wherein the latter is substantially non-coordinating. Non-limitingexamples of ionic activators are boron ionic activators that are fourcoordinate with four ligands bonded to the boron atom. Non-limitingexamples of boron ionic activators include the following formulas shownbelow;

[R₅]⁺[B(R₇)₄]⁻

where B represents a boron atom, R⁵ is an aromatic hydrocarbyl (e.g.triphenyl methyl cation) and each R⁷ is independently selected fromphenyl radicals which are unsubstituted or substituted with from 3 to 5substituents selected from fluorine atoms, C₁₋₄ alkyl or alkoxy radicalswhich are unsubstituted or substituted by fluorine atoms; and a silylradical of formula —Si(R⁹)₃, where each R⁹ is independently selectedfrom hydrogen atoms and C₁₋₄ alkyl radicals, and

[(R⁸)_(t)ZH]⁺[B(R⁷)₄]⁻

where B is a boron atom, H is a hydrogen atom, Z is a nitrogen orphosphorus atom, t is 2 or 3 and R⁸ is selected from C₁₋₈ alkylradicals, phenyl radicals which are unsubstituted or substituted by upto three C₁₋₄ alkyl radicals, or one R⁸ taken together with the nitrogenatom may form an anilinium radical and R⁷ is as defined above.

In both formula a non-limiting example of R⁷ is a pentafluorophenylradical. In general, boron ionic activators may be described as salts oftetra(perfluorophenyl) boron; non-limiting examples include anilinium,carbonium, oxonium, phosphonium and sulfonium salts oftetra(perfluorophenyl)boron with anilinium and trityl (ortriphenylmethylium). Additional non-limiting examples of ionicactivators include: triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammoniumtetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron,trimethylammonium tetra(o-tolyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tributylammoniumtetra(m,m-dimethylphenyl)boron, tributylammoniumtetra(p-trifluoromethylphenyl)boron, tributylammoniumtetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron,N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylaniliniumtetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethylanilinium tetra(phenyl)boron, di-(isopropyl)ammoniumtetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron,triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphoniumtetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron,tropillium tetrakispentafluorophenyl borate, triphenylmethyliumtetrakispentafluorophenyl borate,benzene(diazonium)tetrakispentafluorophenyl borate, tropilliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropilliumtetrakis(1,2,2-trifluoroethenyl)borate, triphenylmethyliumtetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropilliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethyliumtetrakis(2,3,4,5-tetrafluorophenyl)borate, and benzene(diazonium)tetrakis(2,3,4,5 tetrafluorophenyl)borate. Readily available commercialionic activators include N,N-dimethylanilinium tetrakispentafluorophenylborate, and triphenylmethylium tetrakispentafluorophenyl borate.

Non-limiting example of hindered phenols include butylated phenolicantioxidants, butylated hydroxytoluene, 2,6-di-tertiarybutyl-4-ethylphenol, 4,4′-methylenebis (2,6-di-tertiary-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene andoctadecyl-3-(3′,5′-di-tert-butyl-4′-hydroxyphenyl) propionate.

To produce an active single site catalyst system the quantity and moleratios of the three or four components: the single site catalyst, thealkylaluminoxane, the ionic activator, and the optional hindered phenolare optimized.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene produces no long chain branches, and thethird polyethylene will contain no measurable amounts of long chainbranches.

In an embodiment of the disclosure, the single site catalyst used tomake the third polyethylene produces long chain branches, and the thirdpolyethylene will contain long chain branches, hereinafter “LCB”. LCB isa well-known structural phenomenon in polyethylenes and well known tothose of ordinary skill in the art. Traditionally, there are threemethods for LCB analysis, namely, nuclear magnetic resonancespectroscopy (NMR), for example see J. C. Randall, J Macromol. Sci.,Rev. Macromol. Chem. Phys. 1989, 29, 201; triple detection SEC equippedwith a DRI, a viscometer and a low-angle laser light scatteringdetector, for example see W. W. Yau and D. R. Hill, Int. J. Polym. Anal.Charact. 1996; 2:151; and rheology, for example see W. W. Graessley,Acc. Chem. Res. 1977, 10, 332-339. In this disclosure, a long chainbranch is macromolecular in nature, i.e. long enough to be seen in anNMR spectra, triple detector SEC experiments or rheological experiments.

In embodiments of the disclosure, the upper limit on the molecularweight distribution, M_(w)/M_(n) of the third polyethylene may be about2.8, or about 2.5, or about 2.4, or about 2.3, or about 2.2. Inembodiments of the disclosure, the lower limit on the molecular weightdistribution, M_(w)/M_(n) of the third polyethylene may be about 1.4, orabout 1.6, or about 1.7, or about 1.8, or about 1.9.

In embodiments of the disclosure, the third polyethylene has a molecularweight distribution, M_(w)/M_(n) of <2.3, or <2.1, or <2.0 or about 2.0.In embodiments of the disclosure, the third polyethylene has a molecularweight distribution, M_(w)/M_(n) of from about 1.7 to about 2.2.

In an embodiment of the disclosure, the third polyethylene has from 0 to100 short chain branches per thousand carbon atoms (SCB_(PE-3)). Infurther embodiments, the third polyethylene has from 0 to 30 short chainbranches per thousand carbon atoms (SCB_(PE-3)), or from 0 to 20 shortchain branches per thousand carbon atoms (SCB_(PE-3)), or from 0 to 15short chain branches per thousand carbon atoms (SCB_(PE-3)), or from 0to 10 short chain branches per thousand carbon atoms (SCB_(PE-3)), orfrom 0 to 5 short chain branches per thousand carbon atoms (SCB_(PE-3)),or fewer than 5 short chain branches per thousand carbon atoms(SCB_(PE-3)), or fewer than 3 short chain branches per thousand carbonatoms (SCB_(PE-3)), or fewer than 1 short chain branches per thousandcarbon atoms (SCB_(PE-3)), or about zero short chain branches perthousand carbon atoms (SCB_(PE-23)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-3)) is the branching due to the presence of analpha-olefin comonomer in the polyethylene and will for example have twocarbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In embodiments of the disclosure, the upper limit on the density, d3 ofthe third polyethylene may be about 0.985 g/cm³; in some cases about0.975 g/cm³ and; in other cases about 0.965 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d3 of the third polyethylenemay be about 0.921 g/cm³, in some cases about 0.932 g/cm³, and; in othercases about 0.949 g/cm³.

In embodiments of the disclosure the density, d3 of the thirdpolyethylene may be from about 0.921 g/cm³ to about 0.980 g/cm³, or fromabout 0.921 g/cm³ to about 0.975 g/cm³, or from about 0.926 g/cm³ toabout 0.975 g/cm³, or from about 0.930 g/cm³ to about 0.975 g/cm³, orfrom about 0.936 g/cm³ to about 0.975 g/cm³, or from about 0.940 g/cm³to about 0.975 g/cm³, or from about 0.940 g/cm³ to about 0.980 g/cm³, orfrom about 0.945 g/cm³ to about 0.975 g/cm³, or from about 0.950 g/cm³to about 0.975 g/cm³, or from about 0.951 g/cm³ to about 0.975 g/cm³, orfrom about 0.953 g/cm³ to about 0.975 g/cm³, or from about 0.953 g/cm³to about 0.985 g/cm³.

In embodiments of the disclosure the melt index of the thirdpolyethylene I₂ ³ may be from about 0.1 dg/min to about 10000 dg/min, orfrom about 0.1 dg/min to about 5000 dg/min, or from about 1 dg/min toabout 10000 dg/min, or from about 1 dg/min to about 5000 dg/min, or fromabout 1 dg/min to about 2500 dg/min, or from about 1 dg/min to about2000 dg/min, or from about 10 dg/min to about 10000 dg/min, or fromabout 10 dg/min to about 5000 dg/min, or from about 10 dg/min to about2500 dg/min, or from about 10 dg/min to about 1000 dg/min, or from about25 dg/min to about 10000 dg/min, or from about 25 dg/min to about 5000dg/min, or from about 25 dg/min to about 2500 dg/min, or from about 25dg/min to about 1000 dg/min.

In an embodiment of the disclosure, the third polyethylene has a weightaverage molecular weight, M_(w) of from about 10,000 to about 150,000,or from about 10,000 to about 125,000, or from about 15,000 to about100,000, or from about 15,000 to about 90,000, or from about 15,000 toabout 80,000 or from about 20,000 to about 75,000, or from about 20,000to about 90,000, or from about 20,000 to about 80,000, or from about15,000 to about 75,000, or from about 10,000 to about 50,000, or fromabout 15,000 to about 40,000, or from about 12,000 to about 45,000, orfrom about 12,000 to about 40,000, or less than about 100,000, or lessthan about 75,000, or less than about 50,000, or less than about 45,000or less than about 40,000, or less than about 35,000, or less than about30,000.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is less than the weight average molecularweight of the first polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is less than the weight average molecularweight of the fourth polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene is less than the weight average molecularweight of the first polyethylene and the fourth polyethylene.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 25,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 20,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 15,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 10,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 7,500units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 5,000units (in g/mol) of each other.

In an embodiment of the disclosure, the weight average molecular weightof the third polyethylene and the second polyethylene are within 2,500units (in g/mol) of each other.

In embodiments of the disclosure, the upper limit on the weight percent(wt %) of the third polyethylene in the polyethylene composition (i.e.the weight percent of the third polyethylene based on the total weightof the first, the second, the third and the fourth polyethylene) may beabout 75 wt. %, or about 70 wt. %, or about 65 wt. %, or about 60 wt. %,or about 55 wt. %, or about 50 wt. %, or about 45 wt. %, or about 40 wt.% or about 35 wt. %. In embodiments of the disclosure, the lower limiton the wt. % of the third polyethylene in the polyethylene compositionmay be about 1 wt. %, or about 5 wt. %, or about 10 wt. %, or about 15wt. %, or about 20 wt. %.

The Fourth Polyethylene

In an embodiment of the disclosure, the fourth polyethylene is made witha multi-site catalyst system, non-limiting examples of which includeZiegler-Natta catalysts and chromium catalysts, both of which are wellknown in the art.

In an embodiment of the disclosure, the fourth polyethylene is made witha Ziegler-Natta catalyst.

Ziegler-Natta catalyst systems are well known to those skilled in theart. A Ziegler-Natta catalyst may be an in-line Ziegler-Natta catalystsystem or a batch Ziegler-Natta catalyst system. The term “in-lineZiegler-Natta catalyst system” refers to the continuous synthesis of asmall quantity of an active Ziegler-Natta catalyst system andimmediately injecting this catalyst into at least one continuouslyoperating reactor, wherein the catalyst polymerizes ethylene and one ormore optional α-olefins to form an ethylene polymer. The terms “batchZiegler-Natta catalyst system” or “batch Ziegler-Natta procatalyst”refer to the synthesis of a much larger quantity of catalyst orprocatalyst in one or more mixing vessels that are external to, orisolated from, the continuously operating solution polymerizationprocess. Once prepared, the batch Ziegler-Natta catalyst system, orbatch Ziegler-Natta procatalyst, is transferred to a catalyst storagetank. The term “procatalyst” refers to an inactive catalyst system(inactive with respect to ethylene polymerization); the procatalyst isconverted into an active catalyst by adding an alkyl aluminumco-catalyst. As needed, the procatalyst is pumped from the storage tankto at least one continuously operating reactor, wherein an activecatalyst polymerizes ethylene and one or more optional α-olefins to forma polyethylene. The procatalyst may be converted into an active catalystin the reactor or external to the reactor, or on route to the reactor.

A wide variety of compounds can be used to synthesize an activeZiegler-Natta catalyst system. The following describes various compoundsthat may be combined to produce an active Ziegler-Natta catalyst system.Those skilled in the art will understand that the embodiments in thisdisclosure are not limited to the specific compounds disclosed.

An active Ziegler-Natta catalyst system may be formed from: a magnesiumcompound, a chloride compound, a metal compound, an alkyl aluminumco-catalyst and an aluminum alkyl. As will be appreciated by thoseskilled in the art, Ziegler-Natta catalyst systems may containadditional components; a non-limiting example of an additional componentis an electron donor, e.g. amines or ethers.

A non-limiting example of an active in-line (or batch) Ziegler-Nattacatalyst system can be prepared as follows. In the first step, asolution of a magnesium compound is reacted with a solution of achloride compound to form a magnesium chloride support suspended insolution. Non-limiting examples of magnesium compounds include Mg(R¹)₂;wherein the R¹ groups may be the same or different, linear, branched orcyclic hydrocarbyl radicals containing 1 to 10 carbon atoms.Non-limiting examples of chloride compounds include R²Cl; wherein R²represents a hydrogen atom, or a linear, branched or cyclic hydrocarbylradical containing 1 to 10 carbon atoms. In the first step, the solutionof magnesium compound may also contain an aluminum alkyl. Non-limitingexamples of aluminum alkyl include Al(R³)₃, wherein the R³ groups may bethe same or different, linear, branched or cyclic hydrocarbyl radicalscontaining from 1 to 10 carbon atoms. In the second step a solution ofthe metal compound is added to the solution of magnesium chloride andthe metal compound is supported on the magnesium chloride. Non-limitingexamples of suitable metal compounds include M(X)_(n) or MO(X)_(n);where M represents a metal selected from Group 4 through Group 8 of thePeriodic Table, or mixtures of metals selected from Group 4 throughGroup 8; O represents oxygen, and; X represents chloride or bromide; nis an integer from 3 to 6 that satisfies the oxidation state of themetal. Additional non-limiting examples of suitable metal compoundsinclude Group 4 to Group 8 metal alkyls, metal alkoxides (which may beprepared by reacting a metal alkyl with an alcohol) and mixed-ligandmetal compounds that contain a mixture of halide, alkyl and alkoxideligands. In the fourth step a solution of an alkyl aluminum co-catalystis added to the metal compound supported on the magnesium chloride. Awide variety of alkyl aluminum co-catalysts are suitable, as expressedby formula:

Al(R⁴)_(p)(OR⁹)_(q)(X)_(r)

wherein the R⁴ groups may be the same or different, hydrocarbyl groupshaving from 1 to 10 carbon atoms; the OR⁹ groups may be the same ordifferent, alkoxy or aryloxy groups wherein R⁹ is a hydrocarbyl grouphaving from 1 to 10 carbon atoms bonded to oxygen; X is chloride orbromide, and; (p+q+r)=3, with the proviso that p is greater than 0.Non-limiting examples of commonly used alkyl aluminum co-catalystsinclude trimethyl aluminum, triethyl aluminum, tributyl aluminum,dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminumbutoxide, dimethyl aluminum chloride or bromide, diethyl aluminumchloride or bromide, dibutyl aluminum chloride or bromide and ethylaluminum dichloride or dibromide.

The process described in the paragraph above, to synthesize an activein-line (or batch) Ziegler-Natta catalyst system, can be carried out ina variety of solvents; non-limiting examples of solvents include linearor branched C₅ to C₁₂ alkanes or mixtures thereof.

In an embodiment of the disclosure, the fourth polyethylene is anethylene copolymer. Suitable alpha-olefins which may be copolymerizedwith ethylene to give the fourth polyethylene include 1-propene,1-butene, 1-pentene, 1-hexene and 1-octene.

In an embodiment of the disclosure, the fourth polyethylene is anethylene homopolymer.

In an embodiment of the disclosure, the fourth polyethylene is aheterogeneously branched ethylene copolymer.

In an embodiment of the disclosure, the fourth polyethylene is anethylene/1-octene copolymer.

In embodiments of the disclosure, the fourth polyethylene has amolecular weight distribution, M_(w)/M_(n) of ≥2.3, or >2.3, or ≥2.5,or >2.5, or ≥2.7, or >2.7, or ≥2.9, or >2.9, or ≥3.0, or 3.0. Inembodiments of the disclosure, the fourth polyethylene has a molecularweight distribution, M_(w)/M_(n) of from 2.3 to 7.0, or from 2.3 to 6.5,or from 2.3 to 6.0, or from 2.3 to 5.5, or from 2.5 to 7.0, or from 2.5to 6.5, or from 2.5 to 6.0, or from 2.5 to 5.5, or from 2.7 to 7.0, orfrom 2.7 to 6.5, or from 2.7 to 6.0, or from 2.7 to 5.5, or from 2.9 to7.0, or from 2.9 to 6.5, or from 2.9 to 6.0, or from 2.9 to 5.5.

In an embodiment of the disclosure, the fourth polyethylene has from 0to 100 short chain branches per thousand carbon atoms (SCB_(PE-4)). Infurther embodiments, the fourth polyethylene has from 0 to 100 shortchain branches per thousand carbon atoms (SCB_(PE-4)), or from 0 to 75short chain branches per thousand carbon atoms (SCB_(PE-4)), or from 3to 100 short chain branches per thousand carbon atoms (SCB_(PE-4)), orfrom 5 to 75 short chain branches per thousand carbon atoms(SCB_(PE-4)), or from 5 to 50 short chain branches per thousand carbonatoms (SCB_(PE-4)), or from 3 to 50 short chain branches per thousandcarbon atoms (SCB_(PE-4)), or from 5 to 35 short chain branches perthousand carbon atoms (SCB_(PE-4)), or from 3 to 35 short chain branchesper thousand carbon atoms (SCB_(PE-4)).

The short chain branching (i.e. the short chain branching per thousandcarbons, SCB_(PE-4)), if present, is the branching due to the presenceof alpha-olefin comonomer in the polyethylene and will for example havetwo carbon atoms for a 1-butene comonomer, or four carbon atoms for a1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc.

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the fourth polyethylene (SCB_(PE-4)) isgreater than the number of short chain branches per thousand carbonatoms in the second polyethylene (SCB_(PE-2)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the fourth polyethylene (SCB_(PE-4)) isgreater than the number of short chain branches per thousand carbonatoms in the third polyethylene (SCB_(PE-3)).

In an embodiment of the disclosure, the number of short chain branchesper thousand carbon atoms in the fourth polyethylene (SCB_(PE-4)) isgreater than the number of short chain branches per thousand carbonatoms in both the second polyethylene (SCB_(PE-2)) and the thirdpolyethylene (SCB_(PE-3)).

In embodiments of the disclosure, the upper limit on the density, d4 ofthe fourth polyethylene may be about 0.975 g/cm³; in some cases about0.965 g/cm³ and; in other cases about 0.955 g/cm³. In embodiments of thedisclosure, the lower limit on the density, d4 of the fourthpolyethylene may be about 0.855 g/cm³, in some cases about 0.865 g/cm³,and; in other cases about 0.875 g/cm³.

In embodiments of the disclosure the density, d4 of the fourthpolyethylene may be from about 0.875 g/cm³ to about 0.965 g/cm³, or fromabout 0.875 g/cm³ to about 0.960 g/cm³, or from about 0.875 g/cm³ to0.950 g/cm³, or from about 0.865 g/cm³ to about 0.940 g/cm³, or fromabout 0.865 g/cm³ to about 0.936 g/cm³, or from about 0.865 g/cm³ toabout 0.932 g/cm³, or from about 0.865 g/cm³ to about 0.926 g/cm³, orfrom about 0.865 g/cm³ to about 0.921 g/cm³, or from about 0.865 g/cm³to about 0.918 g/cm³, or from about 0.865 g/cm³ to about 0.916 g/cm³, orfrom about 0.875 g/cm³ to about 0.916 g/cm³, or from about 0.865 g/cm³to about 0.912 g/cm³, or from about 0.880 g/cm³ to about 0.912 g/cm³, orfrom about 0.890 g/cm³ to about 0.916 g/cm³, or from about 0.900 g/cm³to about 0.916 g/cm³, or from about 0.880 g/cm³ to about 0.916 g/cm³, orfrom about 0.880 g/cm³ to about 0.918 g/cm³, or from about 0.880 g/cm³to about 0.921 g/cm³, or from about 0.880 g/cm³ to about 0.926 g/cm³, orfrom about 0.880 g/cm³ to about 0.932 g/cm³, or from about 0.880 g/cm³to about 0.936 g/cm³.

In an embodiment of the disclosure, the fourth polyethylene is anethylene copolymer which has a composition distribution breadth index,CDBI₅₀ of 75 wt. % or less, or 70 wt. % or less. In further embodimentsof the disclosure, the fourth polyethylene is an ethylene copolymerwhich has a CDBI₅₀ of 65 wt. % or less, or 60 wt. % or less, or 55 wt. %or less, or 50 wt. % or less, or 45 wt. % or less.

In embodiments of the disclosure the melt index of the fourthpolyethylene I₂ ⁴ may be from about 0.01 dg/min to about 1000 dg/min, orfrom about 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or less than about 5 dg/min, or less than about 3 dg/min, orless than about 1.0 dg/min, or less than about 0.75 dg/min, or less thanabout 0.50 dg/min.

In an embodiment of the disclosure, the fourth polyethylene has a weightaverage molecular weight, M_(w) of from about 50,000 to about 300,000,or from about 50,000 to about 250,000, or from about 60,000 to about250,000, or from about 70,000 to about 250,000, or from about 75,000 toabout 200,000, or from about 80,000 to about 275,000, or from about80,000 to about 250,000, or from about 80,000 to about 200,000, or fromabout 100,000 to about 250,000, or from 70,000 to about 200,000, or fromabout 80,000 to about 175,000, or from about 75,000 to about 195,000, orfrom about 75,000 to about 190,000, or from about 100,000 to about190,000, or from about 100,000 to about 200,000.

In an embodiment of the disclosure, the fourth polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the second polyethylene.

In an embodiment of the disclosure, the fourth polyethylene has a weightaverage molecular weight, M_(w) which is greater than the weight averagemolecular weight, M_(w) of the third polyethylene.

In an embodiment of the disclosure, the fourth polyethylene has a weightaverage molecular weight, M_(w) which is greater than both the weightaverage molecular weight, M_(w) of the second polyethylene and the thirdpolyethylene.

In embodiments of the disclosure, the upper limit on the weight percent(wt. %) of the fourth polyethylene in the polyethylene composition (i.e.the weight percent of the fourth polyethylene based on the total weightof the first, the second, the third, and the fourth polyethylene) may beabout 90 wt. %, or about 85 wt. %, or about 80 wt. %, or about 75 wt. %,or 65 wt. %, in other cases about 60 wt. %, in other cases about 55 wt.%, or about 50 wt. %, or about 45 wt. %. In embodiments of thedisclosure, the lower limit on the wt. % of the fourth polyethylene inthe final polyethylene product may be about 5 wt. %, or about 10 wt. %,or about 15 wt. %, or about 20 wt. %, or about 25 wt. %, or about 30 wt.%, or about 35 wt. %, or in other cases about 40 wt. %.

In embodiments of the disclosure, fourth polyethylene has no long chainbranching present or does not have any detectable levels of long chainbranching.

The Polyethylene Composition

The polyethylene compositions disclosed herein can be made using anywell-known techniques in the art, including but not limited to meltblending, solution blending, or in-reactor blending to bring together afirst polyethylene, a second polyethylene, a third polyethylene and afourth polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending four differentpolyethylene components: i) a first polyethylene, ii) a secondpolyethylene, iii) a third polyethylene, and iv) a fourth polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and a second polyethylene, and ii) second polyethylenecomponent including a third polyethylene and a fourth polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and a third polyethylene, and ii) a second polyethylenecomponent including a second polyethylene and a fourth polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made by melt blending or solution blending two different polyethylenecomponents: i) a first polyethylene component including a firstpolyethylene and a fourth polyethylene, and ii) a second polyethylenecomponent including a second polyethylene and a third polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made using the same single site catalyst in two different reactors,where each reactor is operated under different polymerization conditionsto give a first polyethylene and a second polyethylene, as well as usinga mixed catalyst system including a single site catalyst and amulti-site catalyst in two different reactors, where each reactor isoperated under different or the same polymerization conditions to give athird polyethylene and a fourth polyethylene.

In an embodiment, the polyethylene composition of the present disclosureis made using a different single site catalyst in two differentreactors, where each reactor is operated under similar or differentpolymerization conditions to give a first polyethylene and a secondpolyethylene, as well as using a mixed catalyst system including asingle site catalyst and a multi-site catalyst in two differentreactors, where each reactor is operated under different or the samepolymerization conditions to give a third polyethylene and a fourthpolyethylene.

It is also contemplated by the present disclosure, that the polymercompositions including a first, a second, a third and a fourthpolyethylene could be made in one or more polymerization reactor, usingthree different single site polymerization catalysts and a multi-sitepolymerization catalyst, where each catalyst has a different response toone or more of hydrogen concentration, ethylene concentration, comonomerconcentration, and temperature under a given set of polymerizationconditions, so that the first polyethylene is produced by the firstsingle site catalyst, the second polyethylene is produced by the secondsingle site catalyst, the third polyethylene is produced by the thirdsingle site catalyst and the fourth polyethylene is produced by themulti-site catalyst.

It is also contemplated by the present disclosure, that the polymercompositions including a first, a second, a third and a fourthpolyethylene could be made in one or more polymerization reactors, usingone or more single site polymerization catalysts, and one multi-sitecatalyst, where each catalyst has a similar or different response to oneor more of hydrogen concentration, ethylene concentration, comonomerconcentration, and temperature under a given set of polymerizationconditions, and where one or more of hydrogen concentration, ethyleneconcentration, comonomer concentration, and temperature are cycledthrough a range so that a first, a second, a third and a fourthpolyethylene is produced by the one or more single site catalysts andthe one multi-site catalysts present in the one or more polymerizationreactors.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with single site catalyst,forming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, and forminga fourth polyethylene in a fourth reactor by polymerizing ethylene andoptionally an alpha olefin with a multi-site catalyst.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst,forming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, and forminga fourth polyethylene in a fourth reactor by polymerizing ethylene andoptionally an alpha olefin with a multi-site catalyst, where at leasttwo of the first, second, third and fourth reactors are configured inseries with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, forming a thirdpolyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, and forming a fourth polyethylene in a fourth solution phasepolymerization reactor by polymerizing ethylene and optionally an alphaolefin with a multi-site catalyst.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, forming a thirdpolyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, and forming a fourth polyethylene in a fourth solution phasepolymerization reactor by polymerizing ethylene and optionally an alphaolefin with a multi-site catalyst, where at least two of the first,second, third and fourth solution phase polymerization reactors areconfigured in series with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, forming a thirdpolyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, and forming a fourth polyethylene in a fourth solution phasepolymerization reactor by polymerizing ethylene and optionally an alphaolefin with a multi-site catalyst, where the first and second solutionphase polymerization reactors are configured in series with one anotherand the third and fourth solution phase polymerization reactors areconfigured in series with one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst,forming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst and forming afourth polyethylene in a fourth reactor by polymerizing ethylene andoptionally an alpha olefin with a multi-site catalyst, where each of thefirst, second, third and fourth reactors are configured in parallel toone another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasepolymerization reactor by polymerizing ethylene and an alpha olefin witha single site catalyst; forming a second polyethylene in a secondsolution phase polymerization reactor by polymerizing ethylene andoptionally an alpha olefin with a single site catalyst, forming a thirdpolyethylene in a third solution phase polymerization reactor bypolymerizing ethylene and optionally an alpha olefin with a single sitecatalyst, and forming a fourth polyethylene in a fourth solution phasepolymerization reactor by polymerizing ethylene and optionally an alphaolefin with a multi-site catalyst, where each of the first, second,third and fourth solution phase polymerization reactors are configuredin parallel to one another.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first reactor bypolymerizing ethylene and an alpha olefin with a single site catalyst;forming a second polyethylene in a second reactor by polymerizingethylene and optionally an alpha olefin with a single site catalyst,forming a third polyethylene in a third reactor by polymerizing ethyleneand optionally an alpha olefin with a single site catalyst, and forminga fourth polyethylene in a fourth reactor by polymerizing ethylene andoptionally an alpha olefin with a multi-site catalyst, where the firstand second reactors are configured in series to one another, while thethird and fourth reactors are configured in series to one another andparallel to the first and second reactors.

In an embodiment, the polyethylene composition of the present disclosureis made by forming a first polyethylene in a first solution phasereactor by polymerizing ethylene and an alpha olefin with a single sitecatalyst; forming a second polyethylene in a second solution phasereactor by polymerizing ethylene and optionally an alpha olefin with asingle site catalyst, forming a third polyethylene in a third solutionphase reactor by polymerizing ethylene and optionally an alpha olefinwith a single site catalyst, and forming a fourth polyethylene in afourth solution phase reactor by polymerizing ethylene and optionally analpha olefin with a multi-site catalyst, where the first and secondsolution phase reactors are configured in series to one another, whilethe third and fourth solution phase reactors are configured in series toone another and parallel to the first and second solution phasereactors.

In an embodiment, the solution phase polymerization reactor used as afirst solution phase reactor, a second solution phase reactor, a thirdsolution phase reactor, or a fourth solution phase reactor is acontinuously stirred tank reactor.

In an embodiment, the solution phase polymerization reactor used as afirst solution phase reactor, a second solution phase reactor, a thirdsolution phase reactor, or a fourth solution phase reactor is a tubularreactor.

In a solution phase polymerization reactor, a variety of solvents may beused as the process solvent; non-limiting examples include linear,branched or cyclic C₅ to C₁₂ alkanes. Non-limiting examples of α-olefinsinclude 1-propene, 1-butene, 1-pentene, 1-hexene and 1-octene. Suitablecatalyst component solvents include aliphatic and aromatic hydrocarbons.Non-limiting examples of aliphatic catalyst component solvents includelinear, branched or cyclic C₅₋₁₂ aliphatic hydrocarbons, e.g. pentane,methyl pentane, hexane, heptane, octane, cyclohexane, cyclopentane,methylcyclohexane, hydrogenated naphtha or combinations thereof.Non-limiting examples of aromatic catalyst component solvents includebenzene, toluene (methylbenzene), ethylbenzene, o-xylene(1,2-dimethylbenzene), m-xylene (1,3-dimethylbenzene), p-xylene(1,4-dimethylbenzene), mixtures of xylene isomers, hemellitene(1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene),mesitylene (1,3,5-trimethylbenzene), mixtures of trimethylbenzeneisomers, prehenitene (1,2,3,4-tetramethylbenzene), durene(1,2,3,5-tetramethylbenzene), mixtures of tetramethylbenzene isomers,pentamethylbenzene, hexamethylbenzene and combinations thereof.

In embodiments of the disclosure, the polyethylene composition has adensity which may be from about 0.880 g/cm³ to about 0.965 g/cm³, orfrom about 0.885 g/cm³ to about 0.960 g/cm³, or from about 0.890 g/cm³to 0.950 g/cm³, or from about 0.895 g/cm³ to about 0.940 g/cm³, or fromabout 0.900 g/cm³ to about 0.936 g/cm³, or from about 0.905 g/cm³ toabout 0.934 g/cm³, or from about 0.910 g/cm³ to about 0.932 g/cm³, orfrom about 0.910 g/cm³ to about 0.930 g/cm³, or from about 0.910 g/cm³to about 0.926 g/cm³, or from about 0.890 g/cm³ to about 0.924 g/cm³, orfrom about 0.890 g/cm³ to about 0.922 g/cm³, or from about 0.890 g/cm³to about 0.920 g/cm³, or from about 0.890 g/cm³ to about 0.918 g/cm³, orfrom about 0.880 g/cm³ to about 0.922 g/cm³, or from about 0.880 g/cm³to about 0.926 g/cm³, or from about 0.880 g/cm³ to about 0.932 g/cm³, or≤0.948 g/cm³, or <0.948 g/cm³, or ≤0.945 g/cm³, or <0.945 g/cm³, or≤0.940 g/cm³, or <0.940 g/cm³, or ≤0.939 g/cm³, or <0.939 g/cm³, or≤0.935 g/cm³, or <0.935 g/cm³, or ≤0.932 g/cm³, or <0.932 g/cm³.

In embodiments of the disclosure the melt index I₂ of the polyethylenecomposition may be from about 0.01 dg/min to about 1000 dg/min, or fromabout 0.01 dg/min to about 500 dg/min, or from about 0.01 dg/min toabout 100 dg/min, or from about 0.01 dg/min to about 50 dg/min, or fromabout 0.01 dg/min to about 25 dg/min, or from about 0.01 dg/min to about10 dg/min, or from about 0.01 dg/min to about 5 dg/min, or from about0.01 dg/min to about 3 dg/min, or from about 0.01 dg/min to about 1dg/min, or from about 0.1 dg/min to about 10 dg/min, or from about 0.1dg/min to about 5 dg/min, or from about 0.1 dg/min to about 3 dg/min, orfrom about 0.1 dg/min to about 2 dg/min, or from about 0.1 dg/min toabout 1.5 dg/min, or from about 0.1 dg/min to about 1 dg/min, or lessthan about 5 dg/min, or less than about 3 dg/min, or less than about 1.0dg/min.

In embodiments of the disclosure the high load melt index I₂₁ of thepolyethylene composition may be from about 15 dg/min to about 10,000dg/min, or from about 15 dg/min to about 1000 dg/min, or from about 15dg/min to about 100 dg/min, or from about 15 dg/min to about 75 dg/min,or from about 15 dg/min to about 50 dg/min, or from about 20 dg/min toabout 100 dg/min, or from about 20 dg/min to about 75 dg/min, or fromabout 20 dg/min to about 60 dg/min, or from about 20 dg/min to about 50dg/min, or from about 30 dg/min to about 70 dg/min.

In an embodiment of the disclosure the melt flow ratio I₂₁/I₂ of thepolyethylene composition is >40. In an embodiment of the disclosure themelt flow ratio I₂₁/I₂ of the polyethylene composition >45. Inembodiments of the disclosure the melt flow ratio I₂₁/I₂ of thepolyethylene composition may be from greater than 40 to 120, or fromgreater than 40 to 100, or from 45 to about 90, or from 45 to 80, orfrom greater than 40 to 90.

In embodiments of the disclosure, the polyethylene composition has aweight average molecular weight, M_(w) of from about 50,000 to about300,000, or from about 50,000 to about 250,000, or from about 60,000 toabout 250,000, or from about 70,000 to about 225,000, or from about70,000 to about 200,000, or from about 75,000 to about 175,000, or fromabout 75,000 to about 150,000, or from about 100,000 to about 130,000.

In embodiments of the disclosure, the polyethylene composition has alower limit molecular weight distribution, M_(w)/M_(n) of 2.3, or 2.5,or 2.7, or 2.9. In embodiments of the disclosure, the polyethylenecomposition has an upper limit molecular weight distribution,M_(w)/M_(n) of 8.0, or 7.5, or 7.0, or 6.5, or 6.0, or 5.5. Inembodiments of the disclosure, the polyethylene composition has amolecular weight distribution, M_(w)/M_(n) of from 2.3 to 8.0, or from2.3 to 7.0, or from 2.3 to 6.5, or from 2.3 to 6.0, or from 2.5 to 6.5,or from 2.5 to 6.0, or from 2.5 to 5.5, or from 2.7 to 6.5, or from 2.7to 6.0, or from 2.7 to 5.5.

In embodiments of the disclosure, the polyethylene composition has aZ-average molecular weight distribution, Mz/Mw of ≤5.0, or <5.0, or≤4.5, or <4.5, or ≤4.0, or <4.0, or ≤3.5, or <3.5. In embodiments of thedisclosure, the polyethylene composition has a Z-average molecularweight distribution, Mz/Mw of from 1.5 to 5.5, or from 2.0 to 5.5, orfrom 2 to 5.0, or from 2.0 to 4.5, or from 2.0 to 4.0, or from 2.25 to5.0, or from 2.25 to 4.5, or from 2.25 to 4.0.

In an embodiment of the disclosure, the polyethylene composition has abimodal profile in a gel permeation chromatograph generated according tothe method of ASTM D6474-99. The term “unimodal” is herein defined tomean there will be only one significant peak or maximum evident in theGPC-curve. A unimodal profile includes a broad unimodal profile. Incontrast, the use of the term “bimodal” is meant to convey that inaddition to a first peak, there will be a secondary peak or shoulderwhich represents a higher or lower molecular weight component (i.e. themolecular weight distribution, can be said to have two maxima in amolecular weight distribution curve). Alternatively, the term “bimodal”connotes the presence of two maxima in a molecular weight distributioncurve generated according to the method of ASTM D6474-99. The term“multi-modal” denotes the presence of two or more, typically more thantwo, maxima in a molecular weight distribution curve generated accordingto the method of ASTM D6474-99.

In an embodiment of the disclosure the polyethylene composition may havea multimodal profile in a differential scanning calorimetry (DSC) graph.In the context of DSC analysis, the term “multimodal” connotes a DSCprofile in which two or more distinct melting peaks are observable.

In an embodiment of the disclosure the polyethylene composition may havea bimodal profile in a differential scanning calorimetry (DSC) graph. Inthe context of DSC analysis, the term “bimodal” connotes a DSC profilein which two distinct melting peaks are observable.

In an embodiment of the disclosure, the polyethylene composition has amelting peak temperature in a differential scanning calorimetry (DSC)analysis at above 120° C. For clarity sake, by the phrase “has a meltingpeak temperature in an DSC analysis” it is meant that in a DSC analysis,although there may be one or more melting peaks evident, at least onesuch peak occurs at above the indicated temperature. In an embodiment ofthe disclosure, the polyethylene composition has a melting peaktemperature in a differential scanning calorimetry (DSC) analysis atabove 123° C. In an embodiment of the disclosure, the polyethylenecomposition has a melting peak temperature in a differential scanningcalorimetry (DSC) analysis at above 125° C.

In an embodiment of the disclosure, the polyethylene composition willhave will have a reverse or partially reverse comonomer distributionprofile as measured using GPC-FTIR. If the comonomer incorporationdecreases with molecular weight, as measured using GPC-FTIR, thedistribution is described as “normal”. If the comonomer incorporation isapproximately constant with molecular weight, as measured usingGPC-FTIR, the comonomer distribution is described as “flat” or“uniform”. The terms “reverse comonomer distribution” and “partiallyreverse comonomer distribution” mean that in the GPC-FTIR data obtainedfor a copolymer, there is one or more higher molecular weight componentshaving a higher comonomer incorporation than in one or more lowermolecular weight components. The term “reverse(d) comonomerdistribution” is used herein to mean, that across the molecular weightrange of an ethylene copolymer, comonomer contents for the variouspolymer fractions are not substantially uniform and the higher molecularweight fractions thereof have proportionally higher comonomer contents(i.e. if the comonomer incorporation rises with molecular weight, thedistribution is described as “reverse” or “reversed”). Where thecomonomer incorporation rises with increasing molecular weight and thendeclines, the comonomer distribution is still considered “reverse”, butmay also be described as “partially reverse”. A partially reversecomonomer distribution will exhibit a peak or maximum.

In an embodiment of the disclosure the polyethylene composition has areversed comonomer distribution profile as measured using GPC-FTIR.

In an embodiment of the disclosure the polyethylene composition has apartially reversed comonomer distribution profile as measured usingGPC-FTIR.

In an embodiment of the disclosure, the polyethylene composition has asoluble fraction of at least 7.5 wt. % in a crystallization elutionfractionation (CEF) analysis, where the soluble fraction is defined asthe weight percent (wt. %) of material which elutes at 30° C. and below.In an embodiment of the disclosure, the polyethylene composition has asoluble fraction of at least 10 wt. % in a crystallization elutionfractionation (CEF) analysis, where the soluble fraction is defined asthe weight percent (wt. %) of material which elutes at 30° C. and below.In an embodiment of the disclosure, the polyethylene composition has asoluble fraction of at least 12.5 wt. % in a crystallization elutionfractionation (CEF) analysis, where the soluble fraction is defined asthe weight percent (wt. %) of material which elutes at 30° C. and below.In an embodiment of the disclosure, the polyethylene composition has asoluble fraction of from 7.5 wt. % to 30 wt. % in a crystallizationelution fractionation (CEF) analysis where the soluble fraction isdefined as the weight percent (wt. %) of material which elutes at 30° C.and below. In an embodiment of the disclosure, the polyethylenecomposition has a soluble fraction of from 7.5 wt. % to 25 wt. % in acrystallization elution fractionation analysis. In an embodiment of thedisclosure, the polyethylene composition has a soluble fraction of from7.5 wt. % to 20 wt. % in a crystallization elution fractionation (CEF)analysis. In an embodiment of the disclosure, the polyethylenecomposition has a soluble fraction of from 10 wt. % to 25 wt. % in acrystallization elution fractionation (CEF) analysis. In an embodimentof the disclosure, the polyethylene composition has a soluble fractionof from 10 wt. % to 20 wt. % in a crystallization elution fractionation(CEF) analysis.

In an embodiment of the disclosure, the polyethylene composition has astress exponent, defined as Log₁₀[I₆/I₂]/Log₁₀[6.48/2.16], which is≤1.8. In further embodiments of the disclosure the polyethylenecomposition has a stress exponent, Log₁₀[I₆/I₂]/Log₁₀[6.48/2.16] of lessthan 1.76, or less than 1.70.

In an embodiment of the disclosure, the polyethylene composition has ahexane extractable value of ≤5.0 weight percent, or less than 4.0 wt. %,or less than 3.0 wt. %, or less than 2.0 wt. %, or less than 1.5 wt. %,or less than 1.0 wt. %.

The polyethylene composition disclosed herein may be converted intoflexible manufactured articles such as monolayer or multilayer films,such films are well known to those experienced in the art; non-limitingexamples of processes to prepare such films include blown film and castfilm processes.

In the blown film extrusion process an extruder heats, melts, mixes andconveys a thermoplastic, or a thermoplastic blend. Once molten, thethermoplastic is forced through an annular die to produce athermoplastic tube. In the case of co-extrusion, multiple extruders areemployed to produce a multilayer thermoplastic tube. The temperature ofthe extrusion process is primarily determined by the thermoplastic orthermoplastic blend being processed, for example the melting temperatureor glass transition temperature of the thermoplastic and the desiredviscosity of the melt. In the case of polyolefins, typical extrusiontemperatures are from 330° F. to 550° F. (166° C. to 288° C.). Upon exitfrom the annular die, the thermoplastic tube is inflated with air,cooled, solidified and pulled through a pair of nip rollers. Due to airinflation, the tube increases in diameter forming a bubble of desiredsize. Due to the pulling action of the nip rollers the bubble isstretched in the machine direction. Thus, the bubble is stretched in twodirections: the transverse direction (TD) where the inflating airincreases the diameter of the bubble; and the machine direction (MD)where the nip rollers stretch the bubble. As a result, the physicalproperties of blown films are typically anisotropic, i.e. the physicalproperties differ in the MD and TD directions; for example, film tearstrength and tensile properties typically differ in the MD and TD. Insome instances, the terms “cross direction” or “CD” is used; these termsare equivalent to the terms “transverse direction” or “TD” used in thisdisclosure. In the blown film process, air is also blown on the externalbubble circumference to cool the thermoplastic as it exits the annulardie. The final width of the film is determined by controlling theinflating air or the internal bubble pressure; in other words,increasing or decreasing bubble diameter. Film thickness is controlledprimarily by increasing or decreasing the speed of the nip rollers tocontrol the draw-down rate. After exiting the nip rollers, the bubble ortube is collapsed and may be slit in the machine direction thus creatingsheeting. Each sheet may be wound into a roll of film. Each roll may befurther slit to create film of the desired width. Each roll of film isfurther processed into a variety of consumer products as describedbelow.

The cast film process is similar in that a single or multipleextruder(s) may be used; however the various thermoplastic materials aremetered into a flat die and extruded into a monolayer or multilayersheet, rather than a tube. In the cast film process the extruded sheetis solidified on a chill roll.

Depending on the end-use application, the disclosed polyethylenecomposition may be converted into films that span a wide range ofthicknesses. Non-limiting examples include, food packaging films wherethicknesses may range from about 0.5 mil (13 μm) to about 4 mil (102μm), and; in heavy duty sack applications film thickness may range fromabout 2 mil (51 μm) to about 10 mil (254 μm).

The polyethylene composition disclosed herein may be used in monolayerfilms; where the monolayer may contain more than one polyethylenecomposition and/or additional thermoplastics; non-limiting examples ofthermoplastics include polyethylene polymers and propylene polymers. Thelower limit on the weight percent of the polyethylene composition in amonolayer film may be about 3 wt %, in other cases about 10 wt. % and instill other cases about 30 wt. %. The upper limit on the weight percentof the polyethylene composition in the monolayer film may be 100 wt. %,in other cases about 90 wt. % and in still other cases about 70 wt. %.

The polyethylene composition disclosed herein may also be used in one ormore layers of a multilayer film; non-limiting examples of multilayerfilms include three, five, seven, nine, eleven or more layers. Thethickness of a specific layer (containing the polyethylene composition)within a multilayer film may be about 5%, in other cases about 15% andin still other cases about 30% of the total multilayer film thickness.In other embodiments, the thickness of a specific layer (containing thepolyethylene composition) within a multilayer film may be about 95%, inother cases about 80% and in still other cases about 65% of the totalmultilayer film thickness. Each individual layer of a multilayer filmmay contain more than one polyethylene composition and/or additionalthermoplastics.

Additional embodiments include laminations and coatings, wherein mono ormultilayer films containing the disclosed polyethylene composition areextrusion laminated or adhesively laminated or extrusion coated. Inextrusion lamination or adhesive lamination, two or more substrates arebonded together with a thermoplastic or an adhesive, respectively. Inextrusion coating, a thermoplastic is applied to the surface of asubstrate. These processes are well known to those experienced in theart. Frequently, adhesive lamination or extrusion lamination are used tobond dissimilar materials, non-limiting examples include the bonding ofa paper web to a thermoplastic web, or the bonding of an aluminum foilcontaining web to a thermoplastic web, or the bonding of twothermoplastic webs that are chemically incompatible, e.g. the bonding ofa polyethylene composition containing web to a polyester or polyamideweb. Prior to lamination, the web containing the disclosed polyethylenecomposition(s) may be monolayer or multilayer. Prior to lamination theindividual webs may be surface treated to improve the bonding, anon-limiting example of a surface treatment is corona treating. Aprimary web or film may be laminated on its upper surface, its lowersurface, or both its upper and lower surfaces with a secondary web. Asecondary web and a tertiary web could be laminated to the primary web;wherein the secondary and tertiary webs differ in chemical composition.As non-limiting examples, secondary or tertiary webs may include;polyamide, polyester and polypropylene, or webs containing barrier resinlayers such as EVOH. Such webs may also contain a vapor depositedbarrier layer; for example a thin silicon oxide (SiO_(x)) or aluminumoxide (AlO_(x)) layer. Multilayer webs (or films) may contain three,five, seven, nine, eleven or more layers.

The polyethylene composition disclosed herein can be used in a widerange of manufactured articles including one or more films or filmlayers (monolayer or multilayer). Non-limiting examples of suchmanufactured articles include: food packaging films (fresh and frozenfoods, liquids and granular foods), stand-up pouches, retortablepackaging and bag-in-box packaging; barrier films (oxygen, moisture,aroma, oil, etc.) and modified atmosphere packaging; light and heavyduty shrink films and wraps, collation shrink film, pallet shrink film,shrink bags, shrink bundling and shrink shrouds; light and heavy dutystretch films, hand stretch wrap, machine stretch wrap and stretch hoodfilms; high clarity films; heavy-duty sacks; household wrap, overwrapfilms and sandwich bags; industrial and institutional films, trash bags,can liners, magazine overwrap, newspaper bags, mail bags, sacks andenvelopes, bubble wrap, carpet film, furniture bags, garment bags, coinbags, auto panel films; medical applications such as gowns, draping andsurgical garb; construction films and sheeting, asphalt films,insulation bags, masking film, landscaping film and bags; geomembraneliners for municipal waste disposal and mining applications; batchinclusion bags; agricultural films, mulch film and green house films;in-store packaging, self-service bags, boutique bags, grocery bags,carry-out sacks and t-shirt bags; oriented films, machine direction andbiaxially oriented films and functional film layers in orientedpolypropylene (OPP) films, e.g. sealant and/or toughness layers.Additional manufactured articles including one or more films containingat least one polyethylene composition include laminates and/ormultilayer films; sealants and tie layers in multilayer films andcomposites; laminations with paper; aluminum foil laminates or laminatescontaining vacuum deposited aluminum; polyamide laminates; polyesterlaminates; extrusion coated laminates, and; hot-melt adhesiveformulations. The manufactured articles summarized in this paragraphcontain at least one film (monolayer or multilayer) including at leastone embodiment of the disclosed polyethylene composition.

Desired film physical properties (monolayer or multilayer) typicallydepend on the application of interest. Non-limiting examples ofdesirable film properties include: optical properties (gloss, haze andclarity), dart impact, Elmendorf tear, modulus (1% and 2% secantmodulus), puncture-propagation tear resistance, tensile properties(yield strength, break strength, elongation at break, toughness, etc.)and heat sealing properties (heat seal initiation temperature and hottack strength). Specific hot tack and heat sealing properties aredesired in high speed vertical and horizontal form-fill-seal processesthat load and seal a commercial product (liquid, solid, paste, part,etc.) inside a pouch-like package.

In addition to desired film physical properties, it is desired that thedisclosed polyethylene composition is easy to process on film lines.Those skilled in the art frequently use the term “processability” todifferentiate polymers with improved processability, relative topolymers with inferior processability. A commonly used measure toquantify processability is extrusion pressure; for example, a polymerwith improved processability has a lower extrusion pressure (on a blownfilm or a cast film extrusion line) relative to a polymer with inferiorprocessability.

In an embodiment of the disclosure, a film or film layer includes thepolyethylene composition described above.

In embodiments of the disclosure, a film or film layer includes thepolyethylene composition described above and has a thickness of from 0.5to 10 mil.

In embodiments of the disclosure, a film or film layer has a thicknessof from 0.5 to 10 mil.

In embodiments of the disclosure, a film will have a dart impactstrength of ≥600 g/mil, or ≥650 g/mil, or ≥700 g/mil, or ≥750 g/mil. Inanother embodiment of the disclosure, a film will have a dart impactstrength of from 600 g/mil to 950 g/mil. In a further embodiment of thedisclosure, a film will have dart impact strength of from 650 g/mil to950 g/mil. In a further embodiment of the disclosure, a film will havedart impact strength of from 700 g/mil to 900 g/mil. In a furtherembodiment of the disclosure, a film will have dart impact strength offrom 600 g/mil to 900 g/mil. In yet another embodiment of thedisclosure, the film will have dart impact strength of from 650 g/mil to850 g/mil.

In embodiments of the disclosure, a 1 mil film will have a machinedirection (MD) secant modulus at 1% strain of ≥170 MPa, or ≥180 MPa, or≥190 MPa, or ≥200 MPa, or ≥210 MPa. In another embodiment of thedisclosure, a 1 mil film will have a machine direction (MD) secantmodulus at 1% strain of from 160 MPa to 280 MPa. In an embodiment of thedisclosure, a 1 mil film will have a machine direction (MD) secantmodulus at 1% strain of from 170 MPa to 260 MPa. In an embodiment of thedisclosure, a 1 mil film will have a machine direction (MD) secantmodulus at 1% strain of from 170 MPa to 250 MPa. In another embodimentof the disclosure, a 1 mil film will have a machine direction (MD)secant modulus at 1% strain of from 180 MPa to 240 MPa.

In an embodiment of the disclosure, a 1 mil film will have a transversedirection (TD) secant modulus at 1% strain of ≥200 MPa, or ≥210 MPa, or≥220 MPa, or ≥230 MPa, or ≥240 MPa. In an embodiment of the disclosure,a 1 mil film will have a transverse direction (TD) secant modulus at 1%strain of from 180 MPa to 300 MPa. In another embodiment of thedisclosure, a 1 mil film will have a transverse direction (TD) secantmodulus at 1% strain of from 180 MPa to 290 MPa. In another embodimentof the disclosure, a 1 mil film will have a transverse direction (TD)secant modulus at 1% strain of from 190 MPa to 280 MPa. In anotherembodiment of the disclosure, a 1 mil film will have a transversedirection (TD) secant modulus at 1% strain of from 200 MPa to 300 MPa.In another embodiment of the disclosure, a 1 mil film will have atransverse direction (TD) secant modulus at 1% strain of from 210 MPa to280 MPa. In another embodiment of the disclosure, a 1 mil film will havea transverse direction (TD) secant modulus at 1% strain of from 220 MPato 270 MPa.

In embodiments of the disclosure, a 1 mil film will have a machinedirection (MD) tensile strength at break of ≥36 MPa, or ≥38 MPa, or ≥40MPa, or ≥42 MPa, or ≥44 MPa. In an embodiment of the disclosure, a 1 milfilm will have a machine direction tensile strength at break of from 30MPa to 70 MPa. In an embodiment of the disclosure, a 1 mil film willhave a machine direction (MD) tensile strength at break of from 35 MPato 65 MPa. In another embodiment of the disclosure, a 1 mil film willhave a machine direction (MD) tensile strength at break of from 40 MPato 65 MPa.

In embodiments of the disclosure, a film will have a machine direction(MD) tear strength ≥110 g/mil, or ≥120 g/mil, or ≥130 g/mil, or ≥140g/mil, or ≥150 g/mil, or ≥175 g/mil, or ≥200 g/mil. In an embodiment ofthe disclosure, a film will have a machine direction (MD) tear strengthof from 110 g/mil to 280 g/mil.

In embodiments of the disclosure, a 1 mil film will have a slow punctureresistance value of ≥50 J/mm, or ≥55 J/mm, or ≥60 J/mm, or ≥65 J/mm. Inembodiments of the disclosure, a 1 mil film will have a slow puncturevalue of from 50 J/mm to 90 J/mm, or from 55 J/mm to 90 J/mm, or from 60J/mm to 90 J/mm.

In an embodiment of the disclosure, a 1 mil film will have an oxygentransmission rate (OTR) of ≥550 cm³ per 100 inch². In an embodiment ofthe disclosure, a 1 mil film will have an oxygen transmission rate (OTR)of ≥600 cm³ per 100 inch². In an embodiment of the disclosure, a 1 milfilm will have an oxygen transmission rate (OTR) of ≥650 cm³ per 100inch². In an embodiment of the disclosure, a 1 mil film will have anoxygen transmission rate (OTR) of ≥700 cm³ per 100 inch². In anembodiment of the disclosure, a 1 mil film will have an oxygentransmission rate (OTR) of from 550 to 900 cm³ per 100 inch².

Some embodiments of the present disclosure provide films withimprovements in machine direction (MD) modulus (1% and/or 2%) and oxygentransmission rates (OTRs) relative to films formed from comparativepolyethylene. Hence, in an embodiment of the disclosure, a film layerhaving a thickness of from 0.5 to 10 mil, has a machine direction (MD)1% secant modulus of ≥200 MPa when measured at a film thickness of about1 mil and an oxygen transmission rate (OTR) of ≥550 cm³ per 100 inch²when measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, film satisfies the followingrelationship: oxygen transmission rate (OTR)>−5.4297 (machine direction(MD) 1% secant modulus)+1767.8; where the OTR is measured at a filmthickness of about 1 mil, and the machine direction (MD) 1% secantmodulus is measured at a film thickness of about 1 mil.

In an embodiment of the disclosure, a film layer having a thickness offrom 0.5 to 10 mil, satisfies the following relationships: i) oxygentransmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8, where the OTR is measured at a film thickness of about1 mil, and the machine direction (MD) 1% secant modulus is measured at afilm thickness of about 1 mil.

In an embodiment of the disclosure, a film manufactured using thepolyethylene composition will retain a substantial portion of its darkimpact when downgauged. Accordingly, in an embodiment of the disclosure,a film has a first dart impact value when measured at a film thicknessof about 1 mil, and a second dart impact value when measured at a filmthickness of about 0.75 mil, wherein the second dart impact value iswithin 20 percent of the first dart impact value. In another embodimentof the disclosure, a film has a first dart impact value when measured ata film thickness of about 1 mil, and a second dart impact value whenmeasured at a film thickness of about 0.75 mil, wherein the second dartimpact value is within 17.5 percent of the first dart impact value. Inyet another embodiment of the disclosure, a film has a first dart impactvalue when measured at a film thickness of about 1 mil, and a seconddart impact value when measured at a film thickness of about 0.75 mil,wherein the second dart impact value is within 15 percent of the firstdart impact value. In still yet another embodiment of the disclosure, afilm has a first dart impact value when measured at a film thickness ofabout 1 mil, and a second dart impact value when measured at a filmthickness of about 0.75 mil, wherein the second dart impact value iswithin 12.5 percent of the first dart impact value.

In an embodiment of the disclosure, a film has a first dart impact valuewhen measured at a film thickness of about 1 mil, and a second dartimpact value when measured at a film thickness of about 0.75 mil,wherein the second dart impact value is lower than the first dart impactvalue, but within 20 percent of the first dart impact value. In anotherembodiment of the disclosure, a film has a first dart impact value whenmeasured at a film thickness of about 1 mil, and a second dart impactvalue when measured at a film thickness of about 0.75 mil, wherein thesecond dart impact value is lower than the first dart impact value, butwithin 17.5 percent of the first dart impact value. In yet anotherembodiment of the disclosure, a film has a first dart impact value whenmeasured at a film thickness of about 1 mil, and a second dart impactvalue when measured at a film thickness of about 0.75 mil, wherein thesecond dart impact value is lower than the first dart impact value, butwithin 15 percent of the first dart impact value. In still yet anotherembodiment of the disclosure, a film has a first dart impact value whenmeasured at a film thickness of about 1 mil, and a second dart impactvalue when measured at a film thickness of about 0.75 mil, wherein thesecond dart impact value is lower than the first dart impact value, butwithin 12.5 percent of the first dart impact value.

The films used in the manufactured articles described in this sectionmay optionally include, depending on its intended use, additives andadjuvants. Non-limiting examples of additives and adjuvants include,anti-blocking agents, antioxidants, heat stabilizers, slip agents,processing aids, anti-static additives, colorants, dyes, fillermaterials, light stabilizers, light absorbers, lubricants, pigments,plasticizers, nucleating agents and combinations thereof.

The following examples are presented for the purpose of illustratingselected embodiments of this disclosure; it being understood, that theexamples presented do not limit the claims presented.

EXAMPLES Test Methods

Prior to testing, each specimen was conditioned for at least 24 hours at23±2° C. and 50±10% relative humidity and subsequent testing wasconducted at 23±2° C. and 50±10% relative humidity. Herein, the term“ASTM conditions” refers to a laboratory that is maintained at 23±2° C.and 50±10% relative humidity; and specimens to be tested wereconditioned for at least 24 hours in this laboratory prior to testing.ASTM refers to the American Society for Testing and Materials.

Density was determined using ASTM D792-13 (Nov. 1, 2013).

Melt index was determined using ASTM D1238 (Aug. 1, 2013). Melt indexes,I₂, I₆, I₁₀ and I₂₁ were measured at 190° C., using weights of 2.16 kg,6.48 kg, 10 kg and a 21.6 kg respectively. Herein, the term “stressexponent” or its acronym “S.Ex.”, is defined by the followingrelationship: S.Ex.=log (I₆/I₂)/log(6480/2160); wherein I₆ and I₂ arethe melt flow rates measured at 190° C. using 6.48 kg and 2.16 kg loads,respectively.

M_(n), M_(w), and M_(z) (g/mol) were determined by high temperature GelPermeation Chromatography (GPC) with differential refractive index (DRI)detection using universal calibration (e.g. ASTM-D6474-99). GPC data wasobtained using an instrument sold under the trade name “Waters 150c”,with 1,2,4-trichlorobenzene as the mobile phase at 140° C. The sampleswere prepared by dissolving the polymer in this solvent and were runwithout filtration. Molecular weights are expressed as polyethyleneequivalents with a relative standard deviation of 2.9% for the numberaverage molecular weight (“Mn”) and 5.0% for the weight averagemolecular weight (“Mw”). The molecular weight distribution (MWD) is theweight average molecular weight divided by the number average molecularweight, Mw/M_(n). The z-average molecular weight distribution isM_(z)/M_(n). Polymer sample solutions (1 to 2 mg/mL) were prepared byheating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating on awheel for 4 hours at 150° C. in an oven. The antioxidant2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture in orderto stabilize the polymer against oxidative degradation. The BHTconcentration was 250 ppm. Sample solutions were chromatographed at 140°C. on a PL 220 high-temperature chromatography unit equipped with fourShodex columns (HT803, HT804, HT805 and HT806) using TCB as the mobilephase with a flow rate of 1.0 mL/minute, with a differential refractiveindex (DRI) as the concentration detector. BHT was added to the mobilephase at a concentration of 250 ppm to protect the columns fromoxidative degradation. The sample injection volume was 200 mL. The rawdata were processed with Cirrus GPC software. The columns werecalibrated with narrow distribution polystyrene standards. Thepolystyrene molecular weights were converted to polyethylene molecularweights using the Mark-Houwink equation, as described in the ASTMstandard test method D6474.

The short chain branch frequency (e.g. the short chain branching perthousand backbone carbon atoms, or the SCB/1000C) of ethylene copolymersamples was determined by Fourier Transform Infrared Spectroscopy (FTIR)as per the ASTM D6645-01 method. A Thermo-Nicolet 750 Magna-IRSpectrophotometer equipped with OMNIC version 7.2a software was used forthe measurements. Unsaturations in the polyethylene composition werealso determined by Fourier Transform Infrared Spectroscopy (FTIR) as perASTM D3124-98.

High temperature GPC equipped with an online FTIR detector (GPC-FTIR)was used to measure the comonomer content as the function of molecularweight.

Crystallization Elution Fractionation (CEF): A polymer sample (20 to 25mg) was weighed into the sample vial and loaded onto the auto-sampler ofthe Polymer CEF unit. The vail was filled with 6 to 7 ml1,2,4-trichlorobenzene (TCB), heated to the desired dissolutiontemperature (e.g. 160° C.) with a shaking rate of level number 3 for 2hours. The solution (0.5 ml) was then loaded into the CEF columns (twoCEF columns purchased from Polymer Char and installed in series). Afterallowed to equilibrate at a given stabilization temperature (e.g. 115°C.) for 5 minutes, the polymer solution was allowed to crystallize witha temperature drop from the stabilization temperature to 30° C. Afterequilibrating at 30° C. for 10 minutes, the soluble fraction was elutedat 30° C. for 10 minutes, followed by the crystallized sample elutedwith TCB with a temperature ramp from 30° C. to 110° C. The CEF columnswere cleaned at the end of the run for 5 minutes at 150° C. The otherCEF run conditions were as follows: cooling rate 0.5° C./minute, flowrate in crystallization 0.02 mL/minute, heating rate 1.0° C./minute andflow rate in elution 2.0 mL/minute. The data were processed using Excelspreadsheet. The “CDBI₅₀” is defined as the weight percent of ethylenepolymer whose composition is within 50% of the median comonomercomposition (50% on each side of the median comonomer composition). The“CDBI₅₀” may be calculated from the composition distribution curve,determined by the CEF procedure described above, and the normalizedcumulative integral of the composition distribution curve, asillustrated in U.S. Pat. No. 5,376,439 or WO 93/03093.

The “Composition Distribution Branching Index” or “CDBI” mayalternatively by determined using a crystal-TREF unit commerciallyavailable form Polymer ChAR (Valencia, Spain). The acronym “TREF” refersto Temperature Rising Elution Fractionation. A sample of thepolyethylene composition (80 to 100 mg) was placed in the reactor of thePolymer ChAR crystal-TREF unit, the reactor was filled with 35 ml of1,2,4-trichlorobenzene (TCB), heated to 150° C. and held at thistemperature for 2 hours to dissolve the sample. An aliquot of the TCBsolution (1.5 mL) was then loaded into the Polymer ChAR TREF columnfilled with stainless steel beads and the column was equilibrated for 45minutes at 110° C. The polyethylene composition was then crystallizedfrom the TCB solution, in the TREF column, by slowly cooling the columnfrom 110° C. to 30° C. using a cooling rate of 0.09° C. per minute. TheTREF column was then equilibrated at 30° C. for 30 minutes. Thecrystallized polyethylene composition was then eluted from the TREFcolumn by passing pure TCB solvent through the column at a flow rate of0.75 mL/minute as the temperature of the column was slowly increasedfrom 30° C. to 120° C. using a heating rate of 0.25° C. per minute.Using Polymer ChAR software, a TREF distribution curve was generated asthe polyethylene composition was eluted from the TREF column, i.e. aTREF distribution curve is a plot of the quantity (or intensity) ofpolyethylene composition eluting from the column as a function of TREFelution temperature. A CDBI₅₀ may be calculated from the TREFdistribution curve for each polyethylene composition analyzed. The“CDBI₅₀” is defined as the weight percent of ethylene polymer whosecomposition is within 50% of the median comonomer composition (50% oneach side of the median comonomer composition); it is calculated fromthe TREF composition distribution curve and the normalized cumulativeintegral of the TREF composition distribution curve. Those skilled inthe art will understand that a calibration curve is required to converta TREF elution temperature to comonomer content, i.e. the amount ofcomonomer in the polyethylene composition fraction that elutes at aspecific temperature. The generation of such calibration curves aredescribed for example in Wild, et al., J. Polym. Sci., Part B, Polym.Phys., Vol. 20 (3), pages 441-455: hereby fully incorporated byreference. Note: The “CDBI₂₅” is defined as the weight percent ofpolyethylene composition whose composition is within 25% of the mediancomonomer composition (25% on each side of the median comonomercomposition).

Dynamic mechanical analyses were carried out with a rheometer, namelyRheometrics Dynamic Spectrometer (RDS-II) or Rheometrics SR5 or ATSStresstech, on compression molded samples under nitrogen atmosphere at190° C., using 25 mm diameter cone and plate geometry. The oscillatoryshear experiments were done within the linear viscoelastic range ofstrain (10% strain) at frequencies from 0.05 to 100 rad/s. The values ofstorage modulus (G′), loss modulus (G″), complex modulus (G*) andcomplex viscosity (η*) were obtained as a function of frequency. Thesame rheological data can also be obtained by using a 25 mm diameterparallel plate geometry at 190° C. under nitrogen atmosphere. The Zeroshear viscosity is estimated using the Ellis model, i.e.η(Φ)=η₀/(1+τ/τ_(1/2))^(α−1), where η₀ is the zero shear viscosity.τ_(1/2) is the value of the shear stress at which η=η₀/2 and α is one ofthe adjustable parameters. The Cox-Merz rule is assumed to be applicablein the present disclosure.

The DRI, is the “dow rheology index”, and is defined by the equation:DRI=15 [365000(τ₀/η₀)−1]/10; wherein τ₀ is the characteristic relaxationtime of the polyethylene and η₀ is the zero shear viscosity of thematerial. The DRI is calculated by least squares fit of the rheologicalcurve (dynamic complex viscosity versus applied frequency e.g. 0.01-100rads/s) as described in U.S. Pat. No. 6,114,486 with the followinggeneralized Cross equation, i.e. η(ω)=η₀/[1+(ωτ₀)^(n)]; wherein n is thepower law index of the material, η(ω) and ω are the measured complexviscosity and applied frequency data respectively. When determining theDRI, the zero shear viscosity, η₀ used was estimated with the Ellismodel, rather than the Cross model.

The crossover frequency is the frequency at which storage modulus (G′)and loss modulus (G″) curves cross with each other, while G′@G″=500 Pais the storage modulus at which the loss modulus (G″) is at 500 Pa.

Primary melting peak (° C.), heat of fusion (J/g) and crystallinity (%)was determined using differential scanning calorimetry (DSC) as follows:the instrument was first calibrated with indium; after the calibration,a polymer specimen is equilibrated at 0° C. and then the temperature wasincreased to 200° C. at a heating rate of 10° C./min; the melt was thenkept isothermally at 200° C. for five minutes; the melt was then cooledto 0° C. at a cooling rate of 10° C./min and kept at 0° C. for fiveminutes; the specimen was then heated to 200° C. at a heating rate of10° C./min. The DSC Tm, heat of fusion and crystallinity are reportedfrom the 2^(nd) heating cycle.

Film dart impact strength was determined using ASTM D1709-09 Method A(May 1, 2009). In this disclosure the dart impact test employed a 1.5inch (38 mm) diameter hemispherical headed dart.

The film “ASTM puncture” is the energy (J/mm) required to break the filmwas determined using ASTM D5748-95 (originally adopted in 1995,reapproved in 2012). The puncture test is performed on a mechanicaltester, in which the puncture probe is attached to the load cell whichis mounted on a moving crosshead. The film is clamped into a clampingmechanism which has a 4 inch (102 mm) diameter opening. The clampingmechanism is attached to a fixed plate. The cross head speed is set at10 in/min (255 mm/min). The maximum force and energy to puncture thefilm are recorded.

The “slow puncture” or “lubricated puncture” test was performed asfollows: the energy (J/mm) to puncture a film sample was determinedusing a 0.75-inch (1.9-cm) diameter pear-shaped fluorocarbon coatedprobe travelling at 10-inch per minute (25.4-cm/minute). ASTM conditionswere employed. Prior to testing the specimens, the probe head wasmanually lubricated with Muko Lubricating Jelly to reduce friction. MukoLubricating Jelly is a water-soluble personal lubricant available fromCardinal Health Inc., 1000 Tesma Way, Vaughan, ON L4K 5R8 Canada. Theprobe was mounted in an Instron Model 5 SL Universal Testing Machine anda 1000-N load cell as used. Film samples (1.0 mil (25 μm) thick, 5.5inch (14 cm) wide and 6 inch (15 cm) long) were mounted in the Instronand punctured. The following film tensile properties were determinedusing ASTM D882-12 (Aug. 1, 2012): tensile break strength (MPa),elongation at break (%), tensile yield strength (MPa), tensileelongation at yield (%) and film toughness or total energy to break(ft·lb/in³). Tensile properties were measured in the both the machinedirection (MD) and the transverse direction (TD) of the blown films.

The secant modulus is a measure of film stiffness. The secant modulus isthe slope of a line drawn between two points on the stress-strain curve,i.e. the secant line. The first point on the stress-strain curve is theorigin, i.e. the point that corresponds to the origin (the point of zeropercent strain and zero stress), and; the second point on thestress-strain curve is the point that corresponds to a strain of 1%;given these two points the 1% secant modulus is calculated and isexpressed in terms of force per unit area (MPa). The 2% secant modulusis calculated similarly. This method is used to calculated film modulusbecause the stress-strain relationship of polyethylene does not followHook's law; i.e. the stress-strain behavior of polyethylene isnon-linear due to its viscoelastic nature. Secant moduli were measuredusing a conventional Instron tensile tester equipped with a 200 lbf loadcell. Strips of monolayer film samples were cut for testing withfollowing dimensions: 14 inch long, 1 inch wide and 1 mil thick;ensuring that there were no nicks or cuts on the edges of the samples.Film samples were cut in both the machine direction (MD) and thetransverse direction (TD) and tested. ASTM conditions were used tocondition the samples. The thickness of each film was accuratelymeasured with a hand-held micrometer and entered along with the samplename into the Instron software. Samples were loaded in the Instron witha grip separation of 10 inch and pulled at a rate of 1 inch/mingenerating the strain-strain curve. The 1% and 2% secant modulus werecalculated using the Instron software.

The oxygen transmission rate (OTR) of the blown film was tested using anOxtran 2/20 instrument manufactured by MOCON Inc, Minneapolis, Minn.,USA. The instrument has two test cells (A and B) and each film samplewas analyzed in duplicate. The OTR result reported is the average of theresults from these two test cells (A and B). The test is carried out ata temperature of 23° C. and at a relative humidity of 0%. The filmsample area used for testing was 100 cm². The carrier gas used was 2%hydrogen gas in a balance of nitrogen gas and the test gas is ultra highpurity oxygen. The blown films which were tested each had a filmthickness of 1 mil.

Puncture-propagation tear resistance of blown film was determined usingASTM D2582-09 (May 1, 2009). This test measures the resistance of ablown film to snagging, or more precisely, to dynamic puncture andpropagation of that puncture resulting in a tear. Puncture-propagationtear resistance was measured in the machine direction (MD) and thetransverse direction (TD) of the blown films.

Film tear performance was determined by ASTM D1922-09 (May 1, 2009); anequivalent term for tear is “Elmendorf tear”. Film tear was measured inboth the machine direction (MD) and the transverse direction (TD) of theblown films.

Film optical properties were measured as follows: Haze, ASTM D1003-13(Nov. 15, 2013), and; Gloss ASTM D2457-13 (Apr. 1, 2013).

In this disclosure, the “Hot Tack Test” was performed as follows, usingASTM conditions. Hot tack data was generated using a J&B Hot Tack Testerwhich is commercially available from Jbi Hot Tack, Geloeslaan 30, B-3630Maamechelen, Belgium. In the hot tack test, the strength of a polyolefinto polyolefin seal is measured immediately after heat sealing two filmsamples together (the two film samples were cut from the same roll of2.0 mil (51-μm) thick film), i.e. when the polyolefin macromoleculesthat comprise the film are in a semi-molten state. This test simulatesthe heat sealing of polyethylene films on high speed automatic packagingmachines, e.g., vertical or horizontal form, fill and seal equipment.The following parameters were used in the J&B Hot Tack Test: filmspecimen width, 1 inch (25.4 mm); film sealing time, 0.5 second; filmsealing pressure, 0.27 N/mm²; delay time, 0.5 second; film peel speed,7.9 in/second (200 mm/second); testing temperature range, 131° F. to293° F. (55° C. to 145° C.); temperature increments, 9° F. (5° C.); andfive film samples were tested at each temperature increment to calculateaverage values at each temperature. In this way, a hot tack profile ofpulling force vs sealing temperature is generated. The following datacan be calculated from this hot tack profile: the “Tack Onset @ 1.0 N (°C.)”, is the temperature at which a hot tack force of 1N was observed(an average of five film samples); the “Max Hot tack Strength (N)”, isthe maximum hot tack force observed (an average of five film samples)over the testing temperature range; the “Temperature—Max. Hot tack (°C.)”, is the temperature at which the maximum hot tack force wasobserved. Finally, the area of the hot-tack (strength) window (the “areaof hot tack window” or the “AHTW”) is an estimate of the area under thishot tack profile from the hot-tack on-set temperature to the temperatureimmediately prior to the melting of the specimen. The latter temperatureprior to the melting of the specimen is typically at 130° C., but notnecessarily at 130° C. Piece-wise regressions (linear or polynomial)were performed for different segments of the hot tack profile to obtainthe mathematical relationships between seal temperature and pullingforce. The partial area of each temperature-force segment was thencalculated. The total area (AHTW) is the summation of each partial areaof each segment of the hot tack profile within the specified range(i.e., from the hot-tack on-set temperature to the temperatureimmediately prior to the melting of the specimen).

In this disclosure, the “Heat Seal Strength Test” (also known as “thecold seal test”) was performed as follows. ASTM conditions wereemployed. Heat seal data was generated using a conventional InstronTensile Tester. In this test, two film samples are sealed over a rangeof temperatures (the two film samples were cut from the same roll of 2.0mil (51-μm) thick film). The following parameters were used in the HeatSeal Strength (or cold seal) Test: film specimen width, 1 inch (25.4mm); film sealing time, 0.5 second; film sealing pressure, 40 psi (0.28N/mm²); temperature range, 212° F. to 302° F. (100° C. to 150° C.) andtemperature increment, 9° F. (5° C.). After aging for at least 24 hoursat ASTM conditions, seal strength was determined using the followingtensile parameters: pull (crosshead) speed, 12 inch/min (2.54 cm/min);direction of pull, 90° to seal, and; 5 samples of film were tested ateach temperature increment. The Seal Initiation Temperature, hereafterS.I.T., is defined as the temperature required to form a commerciallyviable seal; a commercially viable seal has a seal strength of 2.0 lbper inch of seal (8.8 N per 25.4 mm of seal).

The hexane extractable content of a polymer sample was determinedaccording to the Code of Federal Registration 21 CFR § 177.1520 Para (c)3.1 and 3.2; wherein the quantity of hexane extractable material in afilm is determined gravimetrically. Elaborating, 2.5 grams of 3.5 mil(89 μm) monolayer film was placed in a stainless steel basket, the filmand basket were weighed (w^(i)), while in the basket the film was:extracted with n-hexane at 49.5° C. for two hours; dried at 80° C. in avacuum oven for 2 hours; cooled in a desiccator for 30 minutes, and;weighed (w^(i)). The percent loss in weight is the percent hexaneextractable (w^(C6)): w^(C6)=100×(w^(i)−w^(i)/w^(i).

Polyethylene Compositions

Polyethylene compositions comprising a first, second, third and fourthpolyethylene were made by melt blending polyethylene compositions A, B,or C with polyethylene compositions D, E or F respectively.

The polyethylene compositions A, B and C were each made using twodifferent single site catalysts in a dual parallel reactor solutionpolymerization process. As a result, polyethylene compositions A, B andC comprised a first polyethylene made with first single site catalyst (ametallocene) and a second polyethylene made with a second single sitecatalyst (a phosphinimine catalyst). A parallel mode solution phasepolymerization reactor process has been described in U.S. patentapplication Ser. No. 15/491,264 (co-pending with the presentapplication). Basically, in parallel mode the exit streams exiting eachof a first reactor (R1) and a second reactor (R2) are combineddownstream of each reactor and the polymer product is obtained afterdevolatilization.

The following examples illustrate the continuous solutioncopolymerization of ethylene and 1-octene at medium pressure in a dualreactor system connected in parallel. The first and second reactorpressure was about 16,000 kPa (about 2.3×10³ psi). The first reactor wasoperated at a lower temperature than the second reactor. The firstreactor had a volume of 12 liters and the second reactor had a volume of24 liters. Both reactors were agitated to ensure good mixing of thereactor contents. The process was continuous in all feed streams (i.e.solvents, which were methyl pentane and xylene; monomers and catalystand cocatalyst components) and in the removal of product. Monomer(ethylene) and comonomer (1-octene) were purified prior to addition tothe reactor using conventional feed preparation systems (such as contactwith various absorption media to remove impurities such as water, oxygenand polar contaminants). The reactor feeds were pumped to the reactorsat the ratios shown in Table 1. Average residence times for the reactorsare calculated by dividing average flow rates by reactor volume. Theresidence time in each reactor for all of the inventive experiments wasless than 10 minutes and the reactors were well mixed. The catalystdeactivator used was octanoic acid (caprylic acid), commerciallyavailable from P&G Chemicals, Cincinnati, Ohio, U.S.A.

The following single site catalyst (SSC) components were used to preparethe first polyethylene in a first reactor (R1) configured in parallel toa second reactor (R2):diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethide [(2,7-tBu₂Flu)Ph₂C(Cp)HfMe₂]; methylaluminoxane (MMAO-07);trityl tetrakis(pentafluoro-phenyl)borate (trityl borate), and2,6-di-tert-butyl-4-ethylphenol (BHEB). Methylaluminoxane (MMAO-07) and2,6-di-tert-butyl-4-ethylphenol are premixed in-line and then combinedwith diphenylmethylene(cyclopentadienyl)(2,7-di-t-butylfuorenyl)hafniumdimethide and trityl tetrakis(pentafluoro-phenyl)borate just beforeentering the polymerization reactor (R1).

The following single site catalyst (SSC) components were used to preparethe second polyethylene in a second reactor (R2) configured in parallelto a first reactor (R1): cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂];methylaluminoxane (MMAO-07); trityl tetrakis(pentafluoro-phenyl)borate(trityl borate), and 2,6-di-tert-butyl-4-ethylphenol (BHEB).Methylaluminoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol arepremixed in-line and then combined with cyclopentadienyltri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂]and trityl tetrakis(pentafluoro-phenyl)borate just before entering thepolymerization reactor (R2).

Polyethylene compositions D, E and F were each made using a mixed dualcatalyst system in a dual parallel reactor solution polymerizationprocess. As a result, polyethylene compositions D, E and F, eachcomprised a third polyethylene made with a single site catalyst (aphosphinimine catalyst) and a fourth polyethylene made with aZiegler-Natta catalyst. A parallel mode solution phase polymerizationreactor process, including one employing a mixed dual catalyst has beendescribed in U.S. patent application Ser. No. 15/491,264 (co-pendingwith the present application). Basically, in parallel mode the exitstreams exiting each of a first reactor (R1) and a second reactor (R2)are combined downstream of each reactor and the polymer product isobtained after devolatilization.

The following examples illustrate the continuous solutioncopolymerization of ethylene and 1-octene at medium pressure in a dualreactor system connected in parallel. The first and second reactorpressure was about 16,000 kPa (about 2.3×10³ psi). The first reactor wasoperated at a lower temperature than the second reactor. The firstreactor had a volume of 12 liters and the second reactor had a volume of24 liters. Both reactors were agitated to ensure good mixing of thereactor contents. The process was continuous in all feed streams (i.e.solvent, which was methyl pentane; monomers and catalyst and cocatalystcomponents) and in the removal of product. Monomer (ethylene) andcomonomer (1-octene) were purified prior to addition to the reactorusing conventional feed preparation systems (such as contact withvarious absorption media to remove impurities such as water, oxygen andpolar contaminants). The reactor feeds were pumped to the reactors atthe ratios shown in Table 1. Average residence times for the reactorsare calculated by dividing average flow rates by reactor volume. Theresidence time in each reactor for all of the inventive experiments wasless than 10 minutes and the reactors were well mixed.

The following single site catalyst (SSC) components were used to preparethe third polyethylene in a second reactor (R2) configured in parallelto a first reactor (R1): cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂];methylaluminoxane (MMAO-07); trityl tetrakis(pentafluoro-phenyl)borate(trityl borate), and 2,6-di-tert-butyl-4-ethylphenol (BHEB).Methylaluminoxane (MMAO-07) and 2,6-di-tert-butyl-4-ethylphenol arepremixed in-line and then combined with cyclopentadienyl tri(tertiarybutyl)phosphinimine titanium dichloride [Cp((t-Bu)₃PN)TiCl₂] and trityltetrakis(pentafluoro-phenyl)borate just before entering thepolymerization reactor (R2).

The following Ziegler-Natta (ZN) catalyst components were used toprepare the fourth polyethylene in a first reactor (R1) configured inparallel to a second reactor (R2): butyl ethyl magnesium; tertiary butylchloride; titanium tetrachloride; diethyl aluminum ethoxide; andtriethyl aluminum. Methylpentane was used as the catalyst componentsolvent and the in-line Ziegler-Natta catalyst formulation was preparedusing the following steps. In step one, a solution of triethylaluminumand butyl ethyl magnesium (Mg:Al=20, mol:mol) was combined with asolution of tertiary butyl chloride and allowed to react for about 30seconds to produce a MgCl₂ support. In step two, a solution of titaniumtetrachloride was added to the mixture formed in step one and allowed toreact for about 14 seconds prior to injection into first reactor (R1).The in-line Ziegler-Natta catalyst was activated in the reactor byinjecting a solution of diethyl aluminum ethoxide into R1. The quantityof titanium tetrachloride added to the reactor is shown in Table 1. Theefficiency of the in-line Ziegler-Natta catalyst formulation wasoptimized by adjusting the mole ratios of the catalyst components.

Table 1, shows the reactor conditions used to make polyethylenecompositions A, B, C, D, E and F. The properties of polyethylenecompositions A, B, C, D, E and F are shown in Table 2.

TABLE 1 Reactor Operating Conditions Blending PE PE PE PE PE PEComponent Composition A Composition B Composition C Composition DComposition E Composition F Description SSC in R1 and SSC in R1 and SSCin R1 ZN in R1 and ZN in R1 and ZN in R1 and SSC in R2 SSC in R2 and SSCin SSC in R2 SSC in R2 SSC in R2 (dual reactor in (dual reactor in R2(dual (dual reactor (dual reactor (dual reactor parallel mode) parallelmode) reactor in in parallel in parallel in parallel parallel mode)mode) mode) mode) Reactor 1 (R1) metallocene metallocene metallocene ZNZN ZN TSR (kg/hr) 370 389.8 367.2 294.9 413.3 273.9 Ethylene 9.5 9.7 9.77.1 9.7 9.3 concentration (wt %) 1-Octene/ethylene 0.53 0.54 0.53 2.430.96 1.18 in fresh feed (g/g) Primary feed 35.0 35.0 35.1 35.0 35.0 35.0temperature (° C.) Mean Temperature 144.4 145.9 145.9 125.3 149.4 146.7(° C.) Ethylene conversion 75.0 72.3 75.4 86.32 87.91 85.02 HydrogenFeed 0.2 5.0 2.0 0.2 1.3 1.0 (ppm) Catalyst (ppm) to R1 0.79 0.59 0.674.40 5.33 3.86 SSC - Al/Hf 31 31 31 N/A N/A N/A (mol/mol) SSC - BHEB/Al0.4 0.4 0.4 N/A N/A N/A (mol/mol) SSC - B/Hf 1.22 1.22 1.22 N/A N/A N/A(mol/mol) ZN - N/A N/A N/A 2.1 2.1 2.1 tertbutylchloride/Mg (mol/mol)ZN - Mg/Ti N/A N/A N/A 7.0 7.0 7.0 (mol/mol) ZN - diethyl N/A N/A N/A1.35 1.35 1.35 aluminum ethoxide/Ti (mol/mol) Reactor 2 (R2)phosphinimine phosphinimine phosphinimine phosphinimine phosphiniminephosphinimine TSR (kg/hr) 155.0 135.2 157.8 305.1 136.8 326.1 Ethylene12.7 13.8 12.7 12.7 13.8 12.7 concentration (wt %) 1-Octene/ethylene 0.00.0 0.0 0.0 0.0 0.0 in fresh feed (g/g) Primary feed 44.9 45.8 45.2 45.044.5 45.0 temperature (° C.) Mean Temperature 189.9 200.3 190.1 190.9200.1 191.1 (° C.) Ethylene conversion 90 90 90 90.5 89.6 90.4 HydrogenFeed 18.5 39.9 13.8 18.5 40.0 13.8 (ppm) Catalyst (ppm) to R2 0.35 0.700.32 0.59 0.97 0.48 SSC - Al/Ti 65 65 65 100 100 100 (mol/mol) SSC -BHEB/Al 0.3 0.3 0.3 0.3 0.3 0.3 (mol/mol) SSC - B/Ti (mol/mol) 1.5 1.51.5 1.2 1.2 1.2

TABLE 2 Blend Component Properties PE PE PE PE PE PE Blending ComponentComposition A Composition B Composition C Composition D Composition EComposition F Description SSC in R1 SSC in R1 SSC in R1 ZN in R1 and ZNin R1 and ZN in R1 and and SSC in and SSC in and SSC in SSC in R2 SSC inR2 SSC in R2 R2 (dual R2 (dual R2 (dual (dual reactor (dual reactor(dual reactor reactor in reactor in reactor in in parallel in parallelin parallel parallel parallel parallel mode) mode) mode) mode) mode)mode) Catalysts SSC/SSC SSC/SSC SSC/SSC ZN/SSC ZN/SSC ZN/SSC Density(g/cm³) 0.9096 0.9088 0.9099 0.937 0.9278 0.9418 Melt Index I₂ (g/10min) 0.32 1.45 0.58 2.04 0.34 3.02 Melt Index I₆ (g/10 min) 2.07 7.083.30 17.9 2.58 19 Melt Index I₁₀ (g/10 min) 4.09 14.3 6.36 42.8 4.7340.9 Melt Index I₂₁ (g/10 min) 20.4 61.2 29.9 221.3 27.2 178.1 Melt FlowRatio 60 42.5 49 109 53 59 (I₂₁/I₂) Stress Exponent 1.64 1.45 1.55 1.971.47 1.68 Melt Flow Ratio 13.00 9.87 11 21 14 13.6 (I₁₀/I₂) BranchFrequency - FTIR Branch Freq/1000 C. 23.5 25.1 23.1 13.2 13.1 7.8Comonomer 1-octene 1-octene 1-octene 1-octene 1-octene 1-octeneComonomer Content 4.70 5 4.60 2.6 2.6 1.60 (mole %) Comonomer Content16.5 17.4 16.2 9.8 9.7 6.0 (weight %) Internal Unsat/100 C. 0.011 0.0110.011 0.008 0.006 0.007 Side Chain 0.005 0.003 0.004 0.001 0.003 0.001Unsat/100 C Terminal Unsat/100 C. 0.007 0.008 0.006 0.009 0.023 0.016GPC - Conventional M_(n) 30775 20218 35034 21735 23696 21618 M_(w)109858 81502 106445 84028 126206 83435 M_(z) 233004 172940 220882 415029385927 367450 Polydispersity Index 3.57 4.03 3.04 3.87 5.33 3.86(M_(w)/M_(n))

The properties of three different polyethylene compositions which wereobtained from melt blending polyethylene composition A with polyethylenecomposition D, B with E, and C with F are provided in Table 3 asInventive Examples 1, 2 and 3. The materials were melt blended using aCoperion ZSK 26 co-rotating twin screw extruder with an L/D of 32:1. Theextruder was fitted with an underwater pelletizer and a Gala spin dryer.The materials were co-fed to the extruder using gravimetric feeders toachieve the desired ratios of polyethylene composition A to polyethyleneD (and B to E and C to F). The blends were compounded using a screwspeed of 200 rpm at an output rate of 15-20 kg/hour and at a melttemperature of 225-230° C.

Data for comparative polyethylene compositions, Comparative Examples 1-9is also included in Table 3. Comparative Example 1 is ELITE® 5400G, aresin commercially available from the Dow Chemical Company. ELITE 5400Ghas a density of about 0.916 g/cm³ and a melt index I₂ of about 1dg/min. Comparative Example 2 is SURPASS® FP117-C, a resin commerciallyavailable from the NOVA Chemicals Corporation. SURPASS FP117-C has adensity of 0.917 g/cm³ and a melt index I₂ of 1 dg/min. ComparativeExamples 3 and 4 are resins made according to U.S. Pat. Appl. Pub. No.2016/0108221. Comparative Example 3 is an ethylene/1-octene copolymer,has a density of about 0.917 g/cm³, a melt index I₂ of about 0.96dg/min, and is made in a multi reactor solution process in which a firstreactor and a second reactor are configured in series with one another.Comparative Example 4 is an ethylene/1-octene copolymer, has a densityof about 0.913 g/cm³, a melt index I₂ of about 0.85 dg/min, and is madein a multi reactor solution process in which a first reactor and asecond reactor are configured in series with one another. ComparativeExample 5 is SCLAIR® FP112-A, a resin commercially available from theNOVA Chemicals Corporation. SCLAIR FP112-A has a density of 0.912 g/cm³and a melt index I₂ of 0.9 dg/min. Comparative Example 6 is EXCEED®1018CA, a resin commercially available from ExxonMobil. EXCEED 1018CAhas a density of about 0.918 g/cm³ and a melt index I₂ of about 0.94dg/min. Comparative Example 7 is MARLEX® D139, a resin commerciallyavailable from ChevronPhillips. MARLEX D139 has a density of about 0.918g/cm³ and a melt index I₂ of about 0.9 dg/min. Comparative Example 8 isSCLAIR® FP120-A, a resin commercially available the NOVA ChemicalsCorporation. FP120-A has a density of 0.920 g/cm³ and a melt index I₂ of1 dg/min. Comparative Example 9 is SCLAIR® FP026-F, a resin commerciallyavailable the NOVA Chemicals Corporation. FP026-F has a density of 0.926g/cm³ and a melt index I₂ of 0.75 dg/min.

TABLE 3 Polyethylene Composition Properties Example No. Inventive 2Inventive 1 (50 wt % PE Inventive 3 (68 wt % PE Composition B/ (75 wt %PE Composition A/ 50 wt % PE Composition C/ 32 wt % PE Composition 25 wt% PE Composition D) E) Composition F) Comp. 1 Comp. 2 Density (g/cm³)0.9175 0.9182 0.9175 0.9159 0.9166 Melt Index I₂ (g/10 min) 0.57 0.820.57 1 0.99 Melt Index I₆ (g/10 min) 3.6 4.17 3.6 4.46 4 Melt Index I₁₀(g/10 min) 7.72 8.65 7.72 8.57 7.57 Melt Index I₂₁ (g/10 min) 43.4 39.743.4 31.3 29 Melt Flow Ratio (I₂₁/I₂) 76 48.7 76 31.4 29.4 StressExponent 1.68 1.49 1.68 1.36 1.27 Melt Flow Ratio (I₁₀/I₂) 13.54 10.613.54 8.61 7.67 Rheological Properties Zero Shear Viscosity - 3894017150 23200 15600 8688 190° C. (Pa-s) Crossover Frequency - 19.48 44.2149.03 110.98 73.56 190° C. (rad/s) DRI 3.90 1.50 3.85 2.41 0.26 G′@G″500Pa = 138.02 62.56 103.48 79.3 22.8 Branch Frequency - FTIR BranchFreq/1000 C 20.5 19.3 19.3 15.2 14.1 Comonomer 1-octene 1-octene1-octene Comonomer Content 4.1 3.9 3.9 3 2.8 (mole %) Comonomer Content(wt %) 14.6 13.8 13.8 11.2 10.4 Internal Unsat/100 C 0.009 0.008 0.0090.003 0.019 Side Chain Unsat/100 C 0.008 0.007 0.008 0.004 0.003Terminal Unsat/100 C 0.008 0.016 0.009 0.029 0.006 CEF Soluble fraction(%), ≤30° C. 15.74 12.44 10.56 2.05 0.77 DSC First Melting Peak (° C.)77.400 88.800 78.500 101 109 Second Melting Peak (° C.) 127.8 125.4126.8 118 112 Third Melting Peak (° C.) 128 122 — Heat of Fusion (J/g)122.6 126.7 128.9 119 123 Crystallinity (%) 42.3 43.7 44.4 41.19 42.29GPC - Conventional M_(n) 24477 19616 33648 36781 33939 M_(w) 11661799254 102277 99802 102503 M_(z) 379399 275187 252041 210866 234321Polydispersity Index 4.76 5.06 3.04 2.71 3.02 (M_(w)/M_(n)) Mz/Mw 3.252.77 2.46 2.11 2.29 Hexane Extractables (%) - 0.87 0.72 0.51 0.54 0.56Plaque Example No. Comp. 3 Comp. 4 Comp. 5 Comp. 6 Density (g/cm³)0.9167 0.913 0.912 0.919 Melt Index I₂ (g/10 min) 0.96 0.85 0.9 0.94Melt Index I₆ (g/10 min) 3.72 3.09 3.16 Melt Index I₁₀ (g/10 min) 6.655.16 Melt Index I₂₁ (g/10 min) 24.4 14.8 Melt Flow Ratio (I₂₁/I₂) 25.421.5 31.4 15.8 Stress Exponent 1.23 1.21 1.34 1.11 Melt Flow Ratio(I₁₀/I₂) 7.24 6.78 5.64 Rheological Properties Zero Shear Viscosity -190° C. (Pa-s) 9433 11350 12990 7731 Crossover Frequency - 190° C.(rad/s) 81.27 98.88 83.76 159.80 DRI 0.23 0.22 0.01 G′@G″500 Pa = 23.932 45.7 8 Branch Frequency - FTIR Branch Freq/1000 C 15.6 17.1 19.2 13.4Comonomer 1-octene 1-octene 1-octene 1-hexene Comonomer Content (mole %)3.1 3.4 3.8 2.7 Comonomer Content (wt %) 11.4 12.7 13.8 9.9 InternalUnsat/100 C 0.009 0.007 0.007 0.002 Side Chain Unsat/100 C 0.006 0.0030.007 0.004 Terminal Unsat/100 C 0.046 0.027 0.045 0.01 CEF Solublefraction (%), ≤30° C. 3.78 2.42 7.13 0.57 DSC First Melting Peak (° C.)105.7 100.0 102.0 109.52 Second Melting Peak (° C.) 117.4 119.3 117.9118.08 Third Melting Peak (° C.) 121.2 122.8 121.6 — Heat of Fusion(J/g) 123.9 112.6 110.6 126.96 Crystallinity (%) 42.72 38.82 38.14 43.78GPC - Conventional M_(n) 33939 44573 33139 55850 M_(w) 102503 114666118358 110641 M_(z) 234321 262824 379353 186289 Polydispersity Index(M_(w)/M_(n)) 3.02 2.57 3.57 1.98 Mz/Mw 2.29 2.29 3.21 1.68 HexaneExtractables (%) - Plaque 0.77 0.61 1.40 0.26 Example No. Comp. 7 Comp.8 Comp. 9 Density (g/cm³) 0.918 0.920 0.926 Melt Index I₂ (g/10 min)0.89 1 0.75 Melt Index I₆ (g/10 min) 3.14 4.29 3.02 Melt Index I₁₀ (g/10min) 5.22 — — Melt Index I₂₁ (g/10 min) 15.2 29.8 20.1 Melt Flow Ratio(I₂₁/I₂) 17.2 29.8 27 Stress Exponent 1.15 1.32 1.31 Melt Flow Ratio(I₁₀/I₂) 5.94 — — Rheological Properties Zero Shear Viscosity - 190° C.(Pa-s) 9198 10783 14750 Crossover Frequency - 190° C. (rad/s) 149.38107.5 91.93 DRI 0.09 — — G′@G″500 Pa = 34.1 41.9 47.7 Branch Frequency -FTIR Branch Freq/1000 C 13.1 Comonomer 1-hexene 1-octene 1-octeneComonomer Content (mole %) 2.6 2.6 1.7 Comonomer Content (wt %) 9.7 9.76.3 Internal Unsat/100 C 0.006 0.005 0.002 Side Chain Unsat/100 C 0.0050.006 0.004 Terminal Unsat/100 C 0.007 0.052 0.048 CEF Soluble fraction(%), ≤30° C. 0.57 2.85 1.14 DSC First Melting Peak (° C.) 106.26 108.93115.24 Second Melting Peak (° C.) 116.62 119.52 121.5 Third Melting Peak(° C.) — — Heat of Fusion (J/g) 125.56 132.95 144.24 Crystallinity (%)43.29 45.84 49.74 GPC - Conventional M_(n) 55399 31575 35549 M_(w)106175 101954 112255 M_(z) 180670 302775 297745 Polydispersity Index(M_(w)/M_(n)) 1.92 3.40 3.16 Mz/Mw 1.70 2.82 2.65 Hexane Extractables(%) - Plaque 0.37 0.44 0.22

Details of the Inventive polyethylene composition components: the firstpolyethylene, the second polyethylene, the third polyethylene, and thefourth polyethylene are provided in Table 4. With the exception of theweight percentages, w1, w2, w3 and w4 (which are found by adjusting thede-convoluted values, w1′, w2′, w3′, and w4′ as is further discussedbelow) the data in Table 4 includes the mathematically de-convolutedcomponent properties of polyethylene compositions A, B and C (whichcomprised the first polyethylene which was made with a single sitemetallocene catalyst and the second polyethylene which was made with asingle site phosphinimine catalyst) as well as the mathematicallyde-convoluted component properties of polyethylene compositions D, E andF (which comprised the third polyethylene which was made with a singlesite phosphinimine catalyst and the fourth polyethylene which was madewith a multi site Ziegler-Natta catalyst).

Deconvolution of Polyethylene Compositions A, B and C

High temperature GPC equipped with an online FTIR detector (GPC-FTIR)was used to measure the comonomer content as a function of molecularweight. In order to de-convolute the polyethylene compositions A, B andC (which result from the use of a SSC in R1 and R2 in parallel modepolymerization) into components, the mathematical deconvolution modeldescribed in U.S. Pat. No. 8,022,143 was used. The mathematicaldeconvolution of the GPC and GPC-FTIR data, the molecular weightdistribution of the first polyethylene (the SSC component made in R1,considered one catalyst site) and the second polyethylene (the SSCcomponent made in R2, considered on catalyst site) was modeled using asingle Schultz Flory distribution (where the M_(w)/M_(n) was assumed tobe 2; the M_(n) was M_(w)/2 and the M_(z) was 1.5×Mw) as described inU.S. Pat. No. 8,022,143. To improve the deconvolution accuracy andconsistency, as a constraint, the melt index, I₂, of the modeledcomposition (i.e. the dual-reactor polyethylene composition A, B or C)was set and the following relationship was satisfied during thedeconvolution:

Log₁₀(I ₂)=22.326528+0.003467*[Log₁₀(M _(n))]³−4.322582*Log₁₀(M_(w))−0.180061*[Log₁₀(M _(z))]²+0.026478*[Log₁₀(M _(z))]³

where the experimentally measured overall melt index (i.e. ofpolyethylene composition A, B or C), I₂, was used on the left side ofthe equation. Hence, a total of two sites (one for each SSC) were usedto de-convolute polyethylene composition A, B or C. The w(i) and Mn(i),i=1 to 2, were obtained while Mw(i) and Mz(i) of each site werecalculated using the above relationships using Mn(i) for each site.During the deconvolution, the overall M_(n), M_(w) and M_(z) ofpolyethylene composition A, B or C was calculated with the followingrelationships: M_(n)=1/Sum(w_(i)/M_(n)(i)), M_(w)=Sum(w_(i)×M_(w)(i)),M_(z)=Sum(w_(i)×M_(z)(i)²), where i represents the i-th component andw_(i) represents the relative weight fraction of the i-th component inthe composition from the above 2-site deconvolution. The GPC-FTIRchromatograph profile was subsequently deconvoluted using the w(i)results to obtain SCB(i), i=1 to 2.

The M_(n), M_(w), M_(z) and SCB/1000C of the first and secondpolyethylenes made with a SSC in each of R1 and R2 were then calculatedusing the above relationships, with the above data of Mn(i), Mw(i),Mz(i), SCB(i) for each catalyst site.

When the polymer made with the single site catalyst in R₂ was anethylene homopolymer, as is the case in the present examples, thenduring the deconvolution analysis the SCB/1000C for the modeled SSC sitewas set as zero. If however, the polymer made by the SSC was acopolymer, then the SCB value would be determined for the SSC site usingthe deconvolution model presented above.

In order to calculate the melt index, I₂ of each of the first and secondpolyethylenes in polyethylene composition A, B, or C, the following meltindex, I₂ model was used:

Log₁₀(melt index,I ₂)=22.326528+0.003467*[Log₁₀(M_(n))]³−4.322582*Log₁₀(M _(w))−0.180061*[Log₁₀(M_(z))]²+0.026478*[Log₁₀(M _(z))]³

where the M_(n), M_(w) and M_(z) were the deconvoluted values of thefirst or second polyethylene components present in polyethylenecomposition A, B or C as obtained from the results of the above GPCdeconvolution.

The density of the first polyethylene which was an ethylene copolymermade using a single site catalyst in R1 was calculated using thefollowing density model:

density of the first polyethylene made with aSSC=0.979863−0.00594808*(FTIR SCB/1000C)^(0.65)−0.000383133*[Log₁₀(M_(n))]³−0.00000577986*(M _(w) /M _(n))³+0.00557395*(M _(z) /M_(w))^(0.25)

where the M_(n), M_(w) and M_(z) were the deconvoluted values of thefirst polyethylene as obtained from the results of the above GPCdeconvolution and the SCB/1000C was obtained from the GPC-FTIRdeconvolution. The density of the second polyethylene which was anethylene homopolymer made with a single site catalyst in R₂ wasdetermined using the same equation used above for finding the density ofthe first polyethylene, but with the value for the short chain branchingset to zero to cancel out the corresponding term:

density of the second polyethylene made with aSSC=0.979863−0.000383133*[Log₁₀(M _(n))]³−0.00000577986*(M _(w) /M_(n))³+0.00557395*(M _(z) /M _(w))^(0.25).

The de-convolution provided the density (d1, and d2), melt index (I₂ ¹and I₂ ²), short chain branching (SCB1 with the SCB2 being set as zerofor an ethylene homopolymer) the weight average and number averagemolecular weights (Mw1, Mn1, Mw2 and Mn2), and the weight fraction (w1′and w2′) of the first and second polyethylenes The resultingdeconvoluted properties as well as the relative weight percentages w1,w2 (which for the first and the second polyethylenes, respectively, arefound by modifying the deconvoluted weight fractions w1′ and w2′ tomatch the amount of polyethylene composition A, B or C in the final meltblended polyethylene composition, as determined by the blending rulesdiscussed further below) are provided in Table 4.

Deconvolution of Polyethylene Compositions D, E and F

In order to de-convolute the polyethylene composition D, E of F (whichresult from the use of a ZN catalyst in R1 and a SSC in R2 in parallelmode polymerization) into components, the mathematical deconvolutionmodel described in U.S. Pat. No. 8,022,143 was used but with somemodifications to find the properties of the Ziegler-Natta component (asmade in R1) as is described further below. Here, in the mathematicaldeconvolution of the GPC and GPC-FTIR data, the molecular weightdistribution of the third polyethylene (the SSC component made in R2,considered one catalyst site) was modeled using a single Schultz Florydistribution (where the M_(w)/M_(n) was assumed to be 2; the M_(n) wasMw/2 and the Mz was 1.5×Mw) as described in U.S. Pat. No. 8,022,143,while the molecular weight distribution of the fourth polyethylene whichwas made using a multi-site Ziegler-Natta catalyst in R1, is consideredto have four catalyst sites for the sake of the model, and hence wasmodeled using four Shultz-Flory distributions (each of which had aM_(w)/M_(n) of 2; and where M_(n) was Mw/2 and Mz was 1.5×Mw for eachsite). To improve the deconvolution accuracy and consistency, as aconstraint, the melt index, I₂, of the modeled composition (i.e. thedual-reactor polyethylene composition D, E or F) was set and thefollowing relationship was satisfied during the deconvolution:

Log₁₀(I ₂)=22.326528+0.003467*[Log₁₀(M _(n))]³−4.322582*Log₁₀(M_(w))−0.180061*[Log₁₀(M _(z))]²+0.026478*[Log₁₀(M _(z))]³

where the experimentally measured overall melt index (i.e. ofpolyethylene composition D, E or F), I₂, was used on the left side ofthe equation. Hence, a total of five sites (one for the SSC, i=1; andfour for the ZN, i=2 to 5) were used to de-convolute polyethylenecomposition D, E or F. The w(i) and Mn(i), i=1 to 5, were obtained whileMw(i) and Mz(i) of each site were calculated using the aboverelationships using Mn(i) for each site. Note that the sum of w(i), i=1to 5, is equal to unity. During the deconvolution, the overall M_(n),M_(w) and M_(z) of polyethylene composition D, E, or F were calculatedwith the following relationships: M_(n)=1/Sum(w_(i)/M_(n)(i)),M_(w)=Sum(w_(i)×M_(w)(i)), M_(z)=Sum(w_(i)×M_(z)(i)²), where irepresents the i-th component and w_(i) represents the relative weightfraction of the i-th component in the composition from the above 5-sitedeconvolution. The GPC-FTIR chromatograph profile was subsequentlydeconvoluted using the w(i) results to obtain the short chain branchingin short chain branches per 1000 carbons (the SCB/1000C) for each site:SCB(i), i=1 to 5.

To obtain the overall characteristics of the fourth polyethylene madewith the Ziegler-Natta catalyst in R1, the weight fraction, w of each ofthe four modeled Ziegler-Natta sites from the above overall 5-sitedeconvolution (i=2 to 5) was normalized first (i.e. the weight fractionw of each ZN site was divided by the total weight of the four sites forthe ZN components). The overall M_(n), M_(w), M_(z) and SCB/1000C of thefourth polyethylene made with the ZN catalyst in R1 were then calculatedusing the above relationships, with the above data of Mn(i), Mw(i),Mz(i), SCB(i) and the newly normalized w(i) for each ZN site.

When the polymer made with the single site catalyst in R2 was anethylene homopolymer, as is the case in the present examples, thenduring the deconvolution analysis the SCB/1000C for the modeled SSC sitewas set as zero. If however, the polymer made by the SSC was acopolymer, then the SCB value would be determined for the SSC site usingthe deconvolution model presented above.

In order to calculate the melt index, I₂ of each of the third and fourthpolyethylenes in polyethylene composition D, E or F, the following meltindex, I₂ model was used:

Log₁₀(melt index,I ₂)=22.326528+0.003467*[Log₁₀(M_(n))]³−4.322582*Log₁₀(M _(w))−0.180061*[Log₁₀(M_(z))]²+0.026478*[Log₁₀(M _(z))]³

where the M_(n), M_(w) and M_(z) were the deconvoluted values of thethird or fourth polyethylene components present in polyethylenecomposition D, E or F, as obtained from the results of the above GPCdeconvolution.

The density of the fourth polyethylene which was an ethylene copolymermade using a Ziegler-Natta catalyst was calculated using the followingdensity model:

density of the forth polyethylene made with a ZNcatalyst=0.979863−0.00594808*(FTIRSCB/1000C)^(0.65)−0.000383133*[Log₁₀(M _(n))]³−0.00000577986*(M _(w) /M_(n))³+0.00557395*(M _(z) /M _(w))^(0.25)

where the M_(n), M_(w) and M_(z) were the overall deconvoluted values ofthe fourth polyethylene as obtained from the results of the above GPCdeconvolution and the SCB/1000C was the overall deconvoluted value ofthe fourth polyethylene as obtained from the results of the aboveGPC-FTIR deconvolution. The density of the third polyethylene which wasan ethylene homopolymer made with a single site catalyst in R2 wasdetermined using the same equation used above for finding the density ofthe fourth polyethylene, but with the value for the short chainbranching set to zero to cancel out the corresponding term:

density of the third polyethylene made with aSSC=0.979863−0.000383133*[Log₁₀(M _(n))]³−0.00000577986*(M _(w) /M_(n))³+0.00557395*(M _(z) /M _(w))^(0.25)

The de-convolution provided the density (d3, and d4), melt index (I₂ ³and I₂ ⁴), short chain branching (SCB3 and SCB4, with the SCB3 being setas zero for an ethylene homopolymer) the weight average and numberaverage molecular weights (Mw3, Mn3, Mw4 and Mn4), and the weightfraction (w3′ and w4′) of the third and fourth polyethylenes Theresulting deconvoluted properties as well as the relative weightpercentages w3, w4 (which for the third and the fourth polyethylenes,respectively, are found by modifying the deconvoluted weight fractionsw3′ and w4′ to match the amount of polyethylene composition D, E or F inthe final melt blended polyethylene composition, as determined by theblending rules discussed further below) are provided in Table 4.

The following basic blending rules were used to achieve the desiredpolyethylene compositions comprising a first, a second, a third and afourth polyethylene:

-   -   w1=weight percentage of the first polyethylene in the final        polyethylene composition;    -   w2=weight percentage of the second polyethylene in the final        polyethylene composition;    -   w3=weight percentage of the third polyethylene in the final        polyethylene composition;    -   w4=weight percentage of the fourth polyethylene in the final        polyethylene composition;    -   w1*=weight percentage of polyethylene composition A, B or C in        the melt blend;    -   w2*=weight percentage of polyethylene composition D, E or F in        the melt blend;    -   w1′=weight percentage of the first polyethylene in polyethylene        composition A, B or C (i.e. the w1′ determined from the        mathematical deconvolution of polyethylene composition A, B or        C);    -   w2′=weight percentage of the second polyethylene in polyethylene        composition A, B or C (i.e. the w2′ determined from the        mathematical deconvolution of polyethylene composition A, B or        C);    -   w3′=weight percentage of the third polyethylene in polyethylene        composition D, E or F (i.e. the w3′ determined from the        mathematical deconvolution of polyethylene composition D, E or        F);    -   w4′=weight percentage of the fourth polyethylene in polyethylene        composition D, E or F (i.e. the w4′ determined from the        mathematical deconvolution of polyethylene composition D, E or        F);    -   where,

w1+w2+w3+w4=1;

w1*+w2*=1;

w1′+w2′=1; and

w3′+w4′=1;

so that,

w1=w1*×w1′;

w2=w1*×w2′;

w3=w2*×w3′; and

w4=w2*×w4′.

TABLE 4 Polyethylene Composition Component Properties Example No.Inventive 1 Inventive 2 Inventive 3 Polyethylene Composition Density(g/cm³) 0.9175 0.9182 0.9173 I₂ (dg/min.) 0.57 0.82 0.87 StressExponent. 1.68 1.49 1.54 MFR (I₂₁/I₂) 76 48.7 52 Mn 24477 19616 33648 Mw116617 99254 102277 Mz 379399 275187 202041 Mw/Mn 4.76 5.06 3.04 Mz/Mw3.25 2.77 1.98 The First Polyethylene Catalyst Type 1 Single SiteCatalyst Single Site Catalyst Single Site Catalyst (metallocene)(metallocene) (metallocene) weight fraction, w1 0.406 0.354 0.443 (note:w1′ = 0.597 (note: w1′ = 0.708 (note: w1′ = 0.591 from deconvolution)from deconvolution) from deconvolution) Mn1 93000 56400 79600 Mw1 186000112800 159200 Mw1/Mn1 2 (Mw1/Mn1 < 2.3) 2 (Mw1/Mn1 < 2.3) 2 (Mw1/Mn1 <2.3) short chain branches per 34.5 35.3 38 1000 carbons I₂ ¹ (g/10 min.)0.08 0.53 0.14 d1 (g/cm³) 0.8796 0.8846 0.8776 The Second PolyethyleneCatalyst Type 2 Single Site Catalyst Single Site Catalyst Single SiteCatalyst (phosphinimine) (phosphinimine) (phosphinimine) weightfraction, w2 0.274 0.146 0.307 (note: w2′ = 0.403 (note: w2′ = 0.292(note: w2′ = 0.409 from deconvolution) from deconvolution) fromdeconvolution) Mn2 18000 8300 18600 Mw2 36000 16600 37200 Mw2/Mn2 2(Mw2/Mn2 < 2.3) 2 (Mw2/Mn2 < 2.3) 2 (Mw2/Mn2 < 2.3) short chain branchesper 0 0 0 1000 carbons I₂ ² (g/10 min) 46.95 1147 41 d2 (g/cm³) 0.95650.9629 0.9562 The Third Polyethylene Catalyst Type 3 Single SiteCatalyst Single Site Catalyst Single Site Catalyst (phosphinimine)(phosphinimine) (phosphinimine) weight fraction, w3 0.187 0.144 0.149(note: w1′ = 0.585 (note: w1′ = 0.288 (note: w1′ = 0.595 fromdeconvolution) from deconvolution) from deconvolution) Mn3 13500 1010015700 Mw3 27000 20200 31400 Mw3/Mn3 2 (Mw3/Mn3 < 2.3) 2 (Mw3/Mn3 < 2.3)2 (Mw3/Mn3 < 2.3) short chain branches per 0 0 0 1000 carbons I₂ ³ (g/10min) 151.5 508 81.9 d3 (g/cm³) 0.9590 0.9614 0.9577 The FourthPolyethylene Catalyst Type 4 ZN Catalyst ZN Catalyst ZN Catalyst weightfraction, w4 0.133 0.356 0.101 (note: w2′ = 0.415 (note: w2′ = 0.712(note: w2′ = 0.405 from deconvolution) from deconvolution) fromdeconvolution) Mn4 34400 33400 37800 Mw4 164000 172300 138400 Mw4/Mn44.77 5.15 3.66 (Mw4/Mn4 > 2.3) (Mw4/Mn4 > 2.3) (Mw4/Mn4 > 2.3) shortchain branches per 26.88 16.28 16.44 1000 carbons I₂ ⁴ (g/10 min) 0.140.11 0.26 d4 (g/cm³) 0.9002 0.9142 0.9132

With reference to FIG. 1, a person skilled in the art will recognizethat the inventive polyethylene compositions have a bimodal GPC profile.

With reference to FIG. 2, a person skilled in the art will recognizethat the inventive polyethylene compositions have a partially reversecomonomer incorporation, where the comonomer incorporation first risesas molecular weight increases, and then falls as the molecular weightincreases still further.

With reference to FIG. 3, a person skilled in the art will recognizethat the inventive polyethylene compositions have a multimodal DSCprofile. For Inventive Examples 1 and 2 the DSC profile is bimodal whilefor Example 3 the DSC profile is trimodal.

The data in Table 3, clearly shows that in contrast to each of thecomparative resins, the inventive polyethylene compositions have asignificant amount of material eluting at lower temperature in acrystallization elution fractionation (CEF) analysis. Inventive Examples1, 2 and 3 each have a soluble fraction in a crystallization elutionfractionation (CEF) analysis of greater than 7.5 weight percent(Inventive Example 1, is 15.7 weight percent; Inventive Example 2, is12.4 weight percent; Inventive Example 3, is 10.6 weight percent), whileall of the Comparative Examples 1-9, have a soluble fraction in acrystallization elution fractionation (CEF) analysis (i.e. a fractioneluting at or below 30° C.) of at less than 10 weight percent.

Blown films were generated by using a 2.5-inch Gloucester blown filmline (L/D=24) with a die diameter of 4-inch. The die was coated withpolymer processing aid (PPA) by spiking the line with a highconcentration of PPA masterbatch to avoid melt fracture. The fixedconditions were die gap of 35 mils (0.0889 cm), frost line height ofabout 17 inches and output of 100 lbs/hr. Films were collected underdifferent orientation conditions. The monolayer 1-mil film was producedwith a blow up ratio (BUR) of 2.5 and the 1-mil films were used forobtaining the physical properties of the films. The monolayer 2-mil film(BUR=2.5) was used for obtaining the cold-seal and hot tack profiles.Data for film blown from the polyethylene compositions of the presentdisclosure is provided in Table 5, along with data for films made fromvarious comparative resins.

Comparative Example 1 is a film made from ELITE® 5400G, a resincommercially available from the Dow Chemical Company. ELITE 5400G has adensity of about 0.916 g/cm³ and a melt index I₂ of about 1 dg/min.Comparative Example 2 is a film made from SURPASS® FP117-C, a resincommercially available from the NOVA Chemicals Corporation. SURPASSFP117-C has a density of 0.917 g/cm³ and a melt index I₂ of 1 dg/min.Comparative Examples 3 and 4 are films made from resins made accordingto US Pat. Appl. Pub. No. 2016/0108221. Comparative Example 3 is a filmmade from an ethylene/1-octene copolymer which has a density of about0.917 g/cm³, a melt index I₂ of about 0.96 dg/min, and which was made ina multi reactor solution process in which a first reactor and a secondreactor are configured in series with one another. Comparative Example 4is a film made from an ethylene/1-octene copolymer which has a densityof about 0.913 g/cm³, a melt index I₂ of about 0.85 dg/min, and whichwas made in a multi reactor solution process in which a first reactorand a second reactor are configured in series with one another.Comparative Example 5 is a film made from SCLAIR® FP112-A, a resincommercially available from the NOVA Chemicals Corporation. SCLAIRFP112-A has a density of 0.912 g/cm³ and a melt index I₂ of 0.9 dg/min.Comparative Example 6 is a film made from EXCEED® 1018CA, a resincommercially available from ExxonMobil. EXCEED 1018CA has a density ofabout 0.918 g/cm³ and a melt index I₂ of about 0.94 dg/min. ComparativeExample 7 is a film made from MARLEX® D139, a resin commerciallyavailable from ChevronPhillips. MARLEX D139 has a density of about 0.918g/cm³ and a melt index I₂ of about 0.9 dg/min. Comparative Example 8 isa film made from SCLAIR® FP120-A, a resin commercially available theNOVA Chemicals Corporation. FP120-A has a density of 0.920 g/cm³ and amelt index I₂ of 1 dg/min. Comparative Example 9 is a film made fromSCLAIR® FP026-F, a resin commercially available the NOVA ChemicalsCorporation. FP026-F has a density of 0.926 g/cm³ and a melt index I₂ of0.75 dg/min. Comparative Example 10 is a film made from SURPASS®FPs016-C, a resin commercially available from the NOVA ChemicalsCorporation. SURPASS FPs016-C has a density of 0.916 g/cm³ and a meltindex I₂ of 0.65 dg/min. In Table 5, the Inventive Examples 1, 2 and 3,are films made from the Inventive polyethylene compositions of InventiveExamples 1, 2 and 3.

In addition to the data in Table 5, films having a smaller thicknesswere made for the inventive compositions as well as for selectedcomparative polyethylenes, in order to explore the effect of film gaugeon film toughness (represented here by dart impact strength) andstiffness (as represented by for example the secant modulus). Blownfilms were again generated by using a 2.5-inch Gloucester blown filmline (L/D=24) with a die diameter of 4-inch. The die was coated withpolymer processing aid (PPA) by spiking the line with a highconcentration of PPA masterbatch to avoid melt fracture. The fixedconditions used were a die gap of 35 mils (0.0889 cm), a frost lineheight of about 17 inches and an output of 100 lbs/hr. Films werecollected under different orientation conditions. The monolayer 1-milfilm was produced with a blow up ratio (BUR) of 2.5 and the monolayer0.75-mil film was produced with a blow up ratio (BUR) of 2.0. Theresults of the downgauging experiments are provided in Table 6.

TABLE 5 Film Properties Example No. Inventive PE Inventive PE InventivePE Comparative 1 Composition 1 Composition 2 Composition 3 Film PhysicalProperties Thickness Profile Ave 1 1 1 1.03 Film Toughness Dart Impact(g/mil) 774 764 830 818 Slow Puncture - Lube/Tef (J/mm) 67 78 65 63 ASTMPuncture (J/mm) 96 137 125 97 Film Tear Resistance Tear - MD (g/mil) 136262 212 247 Tear - TD (g/mil) 496 644 548 485 Film Stiffness 1% SecModulus - MD (Mpa) 219 225 231 165 1% Sec Modulus - TD (Mpa) 247 261 246175 2% Sec Modulus - MD (Mpa) 186 190 201 151 2% Sec Modulus - TD (Mpa)208 219 209 155 Film Tensile Strength Tensile Break Str - MD (Mpa) 4844.8 52.2 44 Tensile Break Str - TD (Mpa) 41.7 41.8 38 45.5 Elongationat Break - MD (%) 520 517 564 486 Elongation at Break - TD (%) 693 730696 725 Tensile Yield Str - MD (Mpa) 10.3 10.4 10.4 9.1 Tensile YieldStr - TD (Mpa) 11.2 11.4 11.3 8.7 Tensile Elong at Yield - MD (%) 10 109 13 Tensile Elong at Yield - TD (%) 10 9 10 13 Film Opticals Gloss at45° 9 24 13 64 Haze (%) 55.4 28.5 44.4 7.8 Cold Seal Properties S.I.T. @8.8N Seal Strength (° C.) 116.5 117.2 94.7 100.4 Max Force (N) 27.8 28.427.2 24.9 Temp. @ Max Force (° C.) 160 160 160 150 Hot Tack PropertiesTack Onset @ 1.0N (° C.) - 2 mil film 93 96.5 82.9 92.5 Max HottackStrength (N) - 2 mil film 2.08 3 2.41 5.4 Temperature - Max. Hottack (°C.) - 2 mil 120 125 120 110 film OTR (cm³ per 100 inch²) 759.1 611.8745.8 — Example No. Comparative 2 Comparative 3 Comparative 4Comparative 5 Film Physical Properties Thickness Profile Ave 1.01 1.04 11 Film Toughness Dart Impact (g/mil) 470 812 891 546 Slow Puncture -Lube/Tef (J/mm) 85 98 ASTM Puncture (J/mm) 66 151 84 Film TearResistance Tear - MD (g/mil) 308 293 231 376 Tear - TD (g/mil) 516 540548 580 Film Stiffness 1% Sec Modulus - MD (Mpa) 129 150.4 145 113 1%Sec Modulus - TD (Mpa) 131.4 167.8 134 111 2% Sec Modulus - MD (Mpa) 117141.4 149 136 2% Sec Modulus - TD (Mpa) 123.8 149.2 136 127 Film TensileStrength Tensile Break Str - MD (Mpa) 46.4 45.4 51.8 56.4 Tensile BreakStr - TD (Mpa) 48 44.6 50.6 53.5 Elongation at Break - MD (%) 534 521557 479 Elongation at Break - TD (%) 796 747 751 761 Tensile Yield Str -MD (Mpa) 8.8 9.1 7.9 8 Tensile Yield Str - TD (Mpa) 8.8 8.9 7.6 7.7Tensile Elong at Yield - MD (%) 22 13 10 16 Tensile Elong at Yield - TD(%) 17 14 10 15 Film Opticals Gloss at 45° 50 72 83.8 67 Haze (%) 12 5.82.9 6.8 Cold Seal Properties S.I.T. @ 8.8 N Seal Strength (° C.) 98.898.2 93.5 89.75 Max Force (N) 19.9 23.7 24.4 24.70 Temp. @ Max Force (°C.) 130 160 160 155 Hot Tack Properties Tack Onset @ 1.0 N (° C.) - 2mil film 100.5 95.4 87 78 Max Hottack Strength (N) - 2 mil film 4.1 4.45.1 3.5 Temperature - Max. Hottack (° C.) - 2 mil 115 115 105 120 filmOTR (cm³ per 100 inch²) 662.8 704.6 771.5 845 Example No. Comp. 6 Comp.7 Comp. 8 Comp. 9 Comp. 10 Film Physical Properties Thickness ProfileAve 1.01 1.03 1 1 1 Film Toughness Dart Impact (g/mil) 827 688 214 1561005 Slow Puncture - Lube/Tef (J/mm) 80 77 73 25 100 ASTM Puncture(J/mm) 78.5 78 260 Film Tear Resistance Tear - MD (g/mil) 241 186 384295 327 Tear - TD (g/mil) 358 454 616 640 431 Film Stiffness 1% SecModulus - MD (Mpa) 156.8 177.6 193 243 170 1% Sec Modulus - TD (Mpa)168.8 185 197 252 165 2% Sec Modulus - MD (Mpa) 150.2 166.4 176 213 1462% Sec Modulus - TD (Mpa) 161.4 170.2 179 220 141 Film Tensile StrengthTensile Break Str - MD (Mpa) 50.7 47.8 52.6 38.4 62.6 Tensile BreakStr - TD (Mpa) 61.1 47.8 42.8 35.8 43.7 Elongation at Break - MD (%) 566505 608 707 511 Elongation at Break - TD (%) 741 692 767 729 763 TensileYield Str - MD (Mpa) 9.7 10.1 10.4 12.7 9.4 Tensile Yield Str - TD (Mpa)9.9 9.2 10.4 13.2 8.8 Tensile Elong at Yield - MD (%) 15 16 10.2 10.5 11Tensile Elong at Yield - TD (%) 14 12 10.7 13.2 10 Film Opticals Glossat 45° 39 84 61.7 56 37 Haze (%) 16.2 3.3 11.8 14.0 15.9 Cold SealProperties S.I.T. @ 8.8 N Seal Strength (° C.) 102.8 102.4 107.5 116.0100.40 Max Force (N) 20.6 23.4 26.5 31.9 24.4 Temp. @ Max Force (° C.)140 120 150 180 150 Hot Tack Properties Tack Onset @ 1.0 N (° C.) - 2mil film 101.2 98.6 98.75 106.4 102.4 Max Hottack Strength (N) - 2 milfilm 5.3 5.7 4.16 4.3 3.01 Temperature - Max. Hottack (° C.) - 2 mil 120120 120 140 110 film OTR (cm³ per 100 inch²) 552.2 545.1 650.8 382.4662.75

TABLE 6 Film Downgauging Example No. Inventive 1 Inv. 2 Inv. 3 FilmToughness Dart Impact of 1 mil film (g/mil) 774 764 830 Dart Impact of0.75 mil film (g/mil) 814 680 742 Change in Dart Impact +5.2% −11%−10.6% Film Stiffness 1% Sec Modulus - MD of 1 mil film 219 225 231(Mpa) 1% Sec Modulus - MD of 0.75 mil 230 233 213 film (Mpa) Change instiffness   +5% +3.6% −7.8% Example No. Comp. 3 Comp. 6 Comp. 7 Comp. 10Film Toughness Dart Impact of 1 mil film 803 853 785 1005 (g/mil) DartImpact of 0.75 mil 582 707 533 587 film (g/mil) Change in Dart Impact−27.5% −17.1% −32.1% −41.6% Film Stiffness 1% Sec Modulus - MD 161 185184 170 of 1 mil film (Mpa) 1% Sec Modulus - MD 168 223 201 161 of 0.75mil film (Mpa) Change in stiffness +4.3% +20.5 +9.2% −5.3%

The data provided in Table 5 together with the data in FIG. 4demonstrate that the inventive polyethylene compositions have a goodbalance of film properties such as good stiffness and good oxygentransmission rates.

FIG. 4 shows that the Inventive Examples 1, 2 and 3 have a betterbalance of OTR and stiffness (as determined by the machine direction(MD) secant modulus at 1% strain) than do the Comparative Examples 2-10.FIG. 4, which plots the OTR (in cm³ per 100 inch²) values (the y-axis)against the machine direction (MD) secant modulus at 1% strain (in MPa)values (the x-axis), along with plot of the equation: OTR=−5.4297(machine direction (MD) 1% secant modulus)+1767.8, shows that theInventive Examples 1, 2 and 3 satisfy the condition: OTR>−5.4297(machine direction (MD) 1% secant modulus)+1767.8, whereas theComparative Examples 2-10 do not.

In addition, and with reference to FIG. 5 and Table 6, film made fromthe inventive polyethylene compositions can be downgauged without aprecipitous drop in dart impact properties.

FIG. 5 shows that for the Inventive Example 1, film having a thicknessof 1 mil has a dart impact strength of 774 g/mil, while film having athickness of 0.75 mil has a dart impact strength of 814 g/mil. Thus, thedart impact of film made from the polyethylene composition of InventiveExample 1 actually increased by 5.2 percent (or by 40 g/mil based on theoriginal dart impact strength of 774 g/mil; 40 g/mil÷774 g/mil×100percent), on downgauging the film from 1 mil to 0.75 mil. For InventiveExamples 2 and 3, the dart impact decreased by 11.0 percent and 10. 6percent on downgauging from a film thickness of 1 mil to 0.75 mil. Incontrast, Comparative Examples 3, 6, 7 and 10s, all have their dartimpacts fall more than 15 percent on downgauging from a film thicknessof 1 mil to 0.75 mil (the dart impact of Comparative Examples 3, 6, 7and 10 falls by 27.5, 17.1, 32.1 and 41.6 percent respectively). Aperson skilled in the art, will recognize that the inventivepolyethylene compositions can be downgauged while better maintainingtheir toughness, thereby requiring less material to achieve a given dartimpact requirement, which improves economics.

Non-limiting embodiments of the present disclosure include thefollowing:

Embodiment A

A polyethylene composition comprising:

from 15 to 75 wt % of a first polyethylene which is an ethylenecopolymer, the first polyethylene having a weight average molecularweight Mw of from 70,000 to 250,000, a molecular weight distributionM_(w)/M_(n) of <2.3 and from 5 to 100 short chain branches per thousandcarbon atoms;

from 5 to 50 wt % of a second polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the second polyethylene having aweight average molecular weight Mw of less than 75,000, a molecularweight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chainbranches per thousand carbon atoms; and

from 5 to 50 wt % of a third polyethylene which is an ethylene copolymeror an ethylene homopolymer, the second polyethylene having a weightaverage molecular weight Mw of less than 75,000, a molecular weightdistribution M_(w)/M_(n) of <2.3 and from 0 to 20 short chain branchesper thousand carbon atoms; and

from 5 to 60 wt % of a fourth polyethylene which is an ethylenecopolymer or an ethylene homopolymer, the fourth polyethylene having aweight average molecular weight Mw of from 100,000 to 250,000, amolecular weight distribution M_(w)/M_(n) of >2.3 and from 0 to 75 shortchain branches per thousand carbon atoms; wherein

the number of short chain branches per thousand carbon atoms in thefirst polyethylene (SCB_(PE-1)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)), the third polyethylene (SCB_(PE-3)) and the fourthpolyethylene (SCB_(PE-4));

the number of short chain branches per thousand carbon atoms in thefourth polyethylene (SCB_(PE-4)) is greater than the number of shortchain branches per thousand carbon atoms in the second polyethylene(SCB_(PE-2)) and the third polyethylene (SCB_(PE-3));

the weight average molecular weight of the second polyethylene and thethird polyethylene are less than the weight average molecular weight ofthe first polyethylene and the fourth polyethylene; and

the weight average molecular weight of the second polyethylene and thethird polyethylene are within 20,000 units of each other; wherein,

the polyethylene composition has a density of ≤0.939 g/cm³, and a meltindex I₂ of from 0.1 to 10 dg/min.

Embodiment B

The polyethylene composition of Embodiment A wherein the polyethylenecomposition has a soluble fraction in a crystallization elutionfractionation (CEF) analysis of at least 7.5 weight percent.

Embodiment C

The polyethylene composition of Embodiment A wherein the polyethylenecomposition has a soluble fraction in a crystallization elutionfractionation (CEF) analysis of at least 10 weight percent.

Embodiment D

The polyethylene composition of Embodiment A, B or C wherein thepolyethylene composition has a melt flow ratio, I₂₁/I₂ of greater than40.

Embodiment E

The polyethylene composition of Embodiment A, B, C or D wherein theweight average molecular weight of the second polyethylene and the thirdpolyethylene are within 15,000 units of each other.

Embodiment F

The polyethylene composition of Embodiment A, B, C or D wherein theweight average molecular weight of the second polyethylene and the thirdpolyethylene are within 10,000 units of each other.

Embodiment G

The polyethylene composition of Embodiment A, B, C, D, E or F whereinthe polyethylene composition has a melting peak temperature in adifferential scanning calorimetry (DSC) analysis at above 125° C.

Embodiment H

The polyethylene composition of Embodiment A, B, C, D, E, F or G whereinthe polyethylene composition has at least two melting peaks in adifferential scanning calorimetry (DSC) analysis.

Embodiment I

The polyethylene composition of Embodiment A, B, C, D, E, F, G or Hwherein the first polyethylene has from 25 to 75 short chain branchesper thousand carbon atoms.

Embodiment J

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H or Iwherein the second polyethylene is an ethylene homopolymer.

Embodiment K

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I orJ wherein the third polyethylene is an ethylene homopolymer.

Embodiment L

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, Jor K wherein the fourth polyethylene is an ethylene copolymer and hasfrom 5 to 35 short chain branches per thousand carbon atoms.

Embodiment M

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K or L wherein the first polyethylene has a weight average molecularweight, Mw of from 75,000 to 200,000.

Embodiment N

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L or M wherein the second polyethylene has a weight average molecularweight, Mw of from 12,000 to 45,000.

Embodiment O

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M or N wherein the third polyethylene has a weight averagemolecular weight, Mw of from 12,000 to 40,000.

Embodiment P

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N or O wherein the fourth polyethylene has a weight averagemolecular weight, Mw of from 100,000 to 200,000.

Embodiment Q

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O or P wherein the first polyethylene has a density of from0.865 to 0.916 g/cm³.

Embodiment R

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P or Q wherein the second polyethylene is an ethylenehomopolymer having a density of from 0.940 to 0.980 g/cm³.

Embodiment S

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q or R wherein the third polyethylene is an ethylenehomopolymer having a density of from 0.940 to 0.980 g/cm³.

Embodiment T

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R or S wherein the fourth polyethylene is anethylene copolymer having a density of from 0.880 to 0.936 g/cm³.

Embodiment U

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S or T wherein the first polyethylene is presentin from 20 to 70 wt %.

Embodiment V

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T or U wherein the second polyethylene ispresent in from 10 to 40 wt %.

Embodiment W

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U or V wherein the third polyethylene ispresent in from 10 to 40 wt %.

Embodiment X

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V or W wherein the fourth polyethyleneis present in from 5 to 50 wt %.

Embodiment Y

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W or X wherein the firstpolyethylene has a CDBI₅₀ of at least 75 wt %.

Embodiment Z

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X or Y wherein the fourthpolyethylene is a copolymer with a CDBI₅₀ of less than 75 wt %.

Embodiment AA

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y or Z wherein the firstpolyethylene is a homogeneously branched ethylene copolymer.

Embodiment BB

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AA wherein the fourthpolyethylene is a heterogeneously branched ethylene copolymer.

Embodiment CC

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA or BB wherein thefirst polyethylene is a made with a single site catalyst.

Embodiment DD

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB or CC wherein thesecond polyethylene is made with a single site catalyst.

Embodiment EE

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC or DD whereinthe third polyethylene is made with a single site catalyst.

Embodiment FF

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD or EEwherein the fourth polyethylene is made with a Ziegler-Natta catalyst.

Embodiment GG

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE or FFwherein the polyethylene composition has a molecular weight distributionM_(w)/M_(n) of from 2.3 to 8.0.

Embodiment HH

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE or FFwherein the polyethylene composition has a molecular weight distributionMw/M_(n) of from 2.5 to 6.5.

Embodiment II

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG or HH wherein the polyethylene composition has a density of <0.935g/cm³.

Embodiment JJ

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG or HH wherein the polyethylene composition has a density of from0.880 to 0.932 g/cm³.

Embodiment KK

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG, HH, II or JJ wherein the polyethylene composition has a melt index,I₂ of from 0.1 to 3.0 dg/min.

Embodiment LL

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG, HH, II, JJ or KK wherein the polyethylene composition has a Mz/M_(w)of less than 4.0.

Embodiment MM

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG, HH, II, JJ, KK or LL wherein the polyethylene composition has a meltindex ratio, I₂₁/I₂ of from greater than 40 to 100.

Embodiment NN

The polyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J,K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF,GG, HH, II, JJ, KK or LL wherein the polyethylene composition has a meltindex ratio, I₂₁/I₂ of greater than 45.

Embodiment OO

A film layer having a thickness of from 0.5 to 10 mil, comprising thepolyethylene composition of Embodiment A, B, C, D, E, F, G, H, I, J, K,L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, GG,HH, II, JJ, KK, LL, MM or NN.

Embodiment PP

The film layer of Embodiment OO wherein the film layer has a machinedirection (MD) 1% secant modulus of ≥200 MPa when measured at a filmthickness of about 1 mil.

Embodiment QQ

The film layer of Embodiment OO or PP wherein the film layer has anoxygen transmission rate (OTR) of ≥550 cm³ per 100 inches² when measuredat a film thickness of about 1 mil.

Embodiment RR

The film layer of Embodiment OO wherein the film layer has a machinedirection (MD) 1% secant modulus of ≥200 MPa when measured at a filmthickness of about 1 mil, and an oxygen transmission rate (OTR) of ≥550cm³ per 100 inches² when measured at a film thickness of about 1 mil.

Embodiment SS

The film layer of Embodiment OO, PP, QQ or RR wherein the film has afirst dart impact value when measured at a film thickness of about 1mil, and a second dart impact value when measured at a film thickness ofabout 0.75 mil, wherein the second dart impact value is within 20percent of the first dart impact value.

Embodiment TT

A film layer having a thickness of from 0.5 to 10 mil, wherein the filmlayer has a machine direction (MD) 1% secant modulus of ≥200 MPa and anoxygen transmission rate (OTR) of ≥550 cm³ per 100 inches² when measuredat a film thickness of about 1 mil.

Embodiment UU

A film layer having a thickness of from 0.5 to 10 mil, wherein the filmhas a first dart impact value when measured at a film thickness of about1 mil, and a second dart impact value when measured at a film thicknessof about 0.75 mil, wherein the second dart impact value is within 20percent of the first dart impact value.

Embodiment VV

A film layer having a thickness of from 0.5 to 10 mil, wherein the filmlayer has a machine direction (MD) 1% secant modulus of ≥200 MPa and anoxygen transmission rate (OTR) of ≥550 cm³ per 100 inches² when measuredat a film thickness of about 1 mil and wherein the film has a first dartimpact value when measured at a film thickness of about 1 mil, and asecond dart impact value when measured at a film thickness of about 0.75mil, wherein the second dart impact value is within 20 percent of thefirst dart impact value.

Embodiment WW

Film comprising the polyethylene composition of Embodiment A, B, C, D,E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA,BB, CC, DD, EE, FF, GG, HH, II, JJ, KK, LL, MM or NN, the filmsatisfying the following relationship:

oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8;

wherein the OTR is measured at a film thickness of about 1 mil, and themachine direction (MD) 1% secant modulus is measured at a film thicknessof about 1 mil.

What is claimed is:
 1. A polyethylene composition comprising: from 15 to75 wt % of a first polyethylene which is an ethylene copolymer, thefirst polyethylene having a weight average molecular weight Mw of from70,000 to 250,000, a molecular weight distribution M_(w)/M_(n) of <2.3and from 5 to 100 short chain branches per thousand carbon atoms; from 5to 50 wt % of a second polyethylene which is an ethylene copolymer or anethylene homopolymer, the second polyethylene having a weight averagemolecular weight Mw of less than 75,000, a molecular weight distributionM_(w)/M_(n) of <2.3 and from 0 to 20 short chain branches per thousandcarbon atoms; and from 5 to 50 wt % of a third polyethylene which is anethylene copolymer or an ethylene homopolymer, the second polyethylenehaving a weight average molecular weight Mw of less than 75,000, amolecular weight distribution M_(w)/M_(n) of <2.3 and from 0 to 20 shortchain branches per thousand carbon atoms; and from 5 to 60 wt % of afourth polyethylene which is an ethylene copolymer or an ethylenehomopolymer, the fourth polyethylene having a weight average molecularweight Mw of from 100,000 to 250,000, a molecular weight distributionM_(w)/M_(n) of >2.3 and from 0 to 75 short chain branches per thousandcarbon atoms; wherein the number of short chain branches per thousandcarbon atoms in the first polyethylene (SCB_(PE-1)) is greater than thenumber of short chain branches per thousand carbon atoms in the secondpolyethylene (SCB_(PE-2)), the third polyethylene (SCB_(PE-3)) and thefourth polyethylene (SCB_(PE-4)); the number of short chain branches perthousand carbon atoms in the fourth polyethylene (SCB_(PE-4)) is greaterthan the number of short chain branches per thousand carbon atoms in thesecond polyethylene (SCB_(PE-2)) and the third polyethylene(SCB_(PE-3)); the weight average molecular weight of the secondpolyethylene and the third polyethylene are less than the weight averagemolecular weight of the first polyethylene and the fourth polyethylene;and the weight average molecular weight of the second polyethylene andthe third polyethylene are within 20,000 units of each other; wherein,the polyethylene composition has a density of ≤0.939 g/cm³, and a meltindex I₂ of from 0.1 to 10 dg/min.
 2. The polyethylene composition ofclaim 1 wherein the polyethylene composition has a soluble fraction in acrystallization elution fractionation (CEF) analysis of at least 7.5weight percent.
 3. The polyethylene composition of claim 1 wherein thepolyethylene composition has a soluble fraction in a crystallizationelution fractionation (CEF) analysis of at least 10 weight percent. 4.The polyethylene composition of claim 1 wherein the polyethylenecomposition has a melt flow ratio, I₂₁/I₂ of greater than
 40. 5. Thepolyethylene composition of claim 1 wherein the weight average molecularweight of the second polyethylene and the third polyethylene are within15,000 units of each other.
 6. The polyethylene composition of claim 1wherein the weight average molecular weight of the second polyethyleneand the third polyethylene are within 10,000 units of each other.
 7. Thepolyethylene composition of claim 1 wherein the polyethylene compositionhas a melting peak temperature in a differential scanning calorimetry(DSC) analysis at above 125° C.
 8. The polyethylene composition of claim1 wherein the polyethylene composition has at least two melting peaks ina differential scanning calorimetry (DSC) analysis.
 9. The polyethylenecomposition of claim 1 wherein the first polyethylene has from 25 to 75short chain branches per thousand carbon atoms.
 10. The polyethylenecomposition of claim 1 wherein the second polyethylene is an ethylenehomopolymer.
 11. The polyethylene composition of claim 1 wherein thethird polyethylene is an ethylene homopolymer.
 12. The polyethylenecomposition of claim 1 wherein the fourth polyethylene is an ethylenecopolymer and has from 5 to 35 short chain branches per thousand carbonatoms.
 13. The polyethylene composition of claim 1 wherein the firstpolyethylene has a weight average molecular weight, Mw of from 75,000 to200,000.
 14. The polyethylene composition of claim 1 wherein the secondpolyethylene has a weight average molecular weight, Mw of from 12,000 to45,000.
 15. The polyethylene composition of claim 1 wherein the thirdpolyethylene has a weight average molecular weight, Mw of from 12,000 to40,000.
 16. The polyethylene composition of claim 1 wherein the fourthpolyethylene has a weight average molecular weight, Mw of from 100,000to 200,000.
 17. The polyethylene composition of claim 1 wherein thefirst polyethylene has a density of from 0.865 to 0.916 g/cm³.
 18. Thepolyethylene composition of claim 1 wherein the second polyethylene isan ethylene homopolymer having a density of from 0.940 to 0.980 g/cm³.19. The polyethylene composition of claim 1 wherein the thirdpolyethylene is an ethylene homopolymer having a density of from 0.940to 0.980 g/cm³.
 20. The polyethylene composition of claim 1 wherein thefourth polyethylene is an ethylene copolymer having a density of from0.880 to 0.936 g/cm³.
 21. The polyethylene composition of claim 1wherein the first polyethylene is present in from 20 to 70 wt %.
 22. Thepolyethylene composition of claim 1 wherein the second polyethylene ispresent in from 10 to 40 wt %.
 23. The polyethylene composition of claim1 wherein the third polyethylene is present in from 10 to 40 wt %. 24.The polyethylene composition of claim 1 wherein the fourth polyethyleneis present in from 5 to 50 wt %.
 25. The polyethylene composition ofclaim 1 wherein the first polyethylene has a CDBI₅₀ of at least 75 wt %.26. The polyethylene composition of claim 1 wherein the fourthpolyethylene is a copolymer with a CDBI₅₀ of less than 75 wt %.
 27. Thepolyethylene composition of claim 1 wherein the first polyethylene is ahomogeneously branched ethylene copolymer.
 28. The polyethylenecomposition of claim 1 wherein the fourth polyethylene is aheterogeneously branched ethylene copolymer.
 29. The polyethylenecomposition of claim 1 wherein the first polyethylene is a made with asingle site catalyst.
 30. The polyethylene composition of claim 1wherein the second polyethylene is made with a single site catalyst. 31.The polyethylene composition of claim 1 wherein the third polyethyleneis made with a single site catalyst.
 32. The polyethylene composition ofclaim 1 wherein the fourth polyethylene is made with a Ziegler-Nattacatalyst.
 33. The polyethylene composition of claim 1 wherein thepolyethylene composition has a molecular weight distribution M_(w)/M_(n)of from 2.3 to 8.0.
 34. The polyethylene composition of claim 1 whereinthe polyethylene composition has a molecular weight distributionMw/M_(n) of from 2.5 to 6.5.
 35. The polyethylene composition of claim 1wherein the polyethylene composition has a density of <0.935 g/cm³. 36.The polyethylene composition of claim 1 wherein the polyethylenecomposition has a density of from 0.880 to 0.932 g/cm³.
 37. Thepolyethylene composition of claim 1 wherein the polyethylene compositionhas a melt index, I₂ of from 0.1 to 3.0 dg/min.
 38. The polyethylenecomposition of claim 1 wherein the polyethylene composition has aMz/M_(w) of less than 4.0.
 39. The polyethylene composition of claim 1wherein the polyethylene composition has a melt index ratio, I₂₁/I₂ offrom greater than 40 to
 100. 40. The polyethylene composition of claim 1wherein the polyethylene composition has a melt index ratio, I₂₁/I₂ ofgreater than
 45. 41. A film layer having a thickness of from 0.5 to 10mil, comprising the polyethylene composition of claim
 1. 42. The filmlayer of claim 41 wherein the film layer has a machine direction (MD) 1%secant modulus of ≥200 MPa when measured at a film thickness of about 1mil.
 43. The film layer of claim 41 wherein the film layer has an oxygentransmission rate (OTR) of ≥550 cm³ per 100 inches² when measured at afilm thickness of about 1 mil.
 44. The film layer of claim 41 whereinthe film layer has a machine direction (MD) 1% secant modulus of ≥200MPa when measured at a film thickness of about 1 mil, and an oxygentransmission rate (OTR) of ≥550 cm³ per 100 inches² when measured at afilm thickness of about 1 mil.
 45. The film layer of claim 41 whereinthe film has a first dart impact value when measured at a film thicknessof about 1 mil, and a second dart impact value when measured at a filmthickness of about 0.75 mil, wherein the second dart impact value iswithin 20 percent of the first dart impact value.
 46. A film layerhaving a thickness of from 0.5 to 10 mil, wherein the film layer has amachine direction (MD) 1% secant modulus of ≥200 MPa and an oxygentransmission rate (OTR) of ≥550 cm³ per 100 inches² when measured at afilm thickness of about 1 mil.
 47. A film layer having a thickness offrom 0.5 to 10 mil, wherein the film has a first dart impact value whenmeasured at a film thickness of about 1 mil, and a second dart impactvalue when measured at a film thickness of about 0.75 mil, wherein thesecond dart impact value is within 20 percent of the first dart impactvalue.
 48. A film layer having a thickness of from 0.5 to 10 mil,wherein the film layer has a machine direction (MD) 1% secant modulus of≥200 MPa and an oxygen transmission rate (OTR) of ≥550 cm³ per 100inches² when measured at a film thickness of about 1 mil and wherein thefilm has a first dart impact value when measured at a film thickness ofabout 1 mil, and a second dart impact value when measured at a filmthickness of about 0.75 mil, wherein the second dart impact value iswithin 20 percent of the first dart impact value.
 49. Film comprisingthe polyethylene composition of claim 1, the film satisfying thefollowing relationship:oxygen transmission rate (OTR)>−5.4297 (machine direction (MD) 1% secantmodulus)+1767.8; wherein the OTR is measured at a film thickness ofabout 1 mil, and the machine direction (MD) 1% secant modulus ismeasured at a film thickness of about 1 mil.